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Organometallics XXXX,XXX,000–000ADOI:10.1021/om100106eNMR Chemical Shifts of Trace Impurities:Common Laboratory Solvents,Organics,and Gases in DeuteratedSolvents Relevant to the OrganometallicChemistGregory R.Fulmer,*,†Alexander ler,‡Nathaniel H.Sherden,‡Hugo E.Gottlieb,§Abraham Nudelman,§Brian M.Stoltz,‡John E.Bercaw,‡andKaren I.Goldberg ††Department of Chemistry,University of Washington,Box 351700,Seattle,Washington 98195-1700,‡Arnold and Mabel Beckman Laboratories of Chemical Synthesis and Caltech Center for Catalysis andChemical Synthesis,Division of Chemistry and Chemical Engineering,California Institute of Technology,Pasadena,California 91125,and §Department of Chemistry,Bar Ilan University,Ramat Gan 52900,IsraelReceived February 11,2010Tables of 1H and 13C NMR chemical shifts have been compiled for common organic compounds often used as reagents or found as products or contaminants in deuterated organic solvents.Building upon the work of Gottlieb,Kotlyar,and Nudelman in the Journal of Organic Chemistry,signals for common impurities are now reported in additional NMR solvents (tetrahydrofuran-d 8,toluene-d 8,dichloromethane-d 2,chlorobenzene-d 5,and 2,2,2-trifluoroethanol-d 3)which are frequently used in organometallic laboratories.Chemical shifts for other organics which are often used as reagents or internal standards or are found as products in organometallic chemistry are also reported for all the listed solvents.Hanging above the desk of most every chemist whose work relies heavily on using NMR spectroscopy 1is NMR Chemi-cal Shifts of Common Laboratory Solvents as Trace Impu-rities by Gottlieb,Kotlyar,and Nudelman.2By compiling the chemical shifts of a large number of contaminants commonly encountered in synthetic chemistry,the publica-tion has become an essential reference,allowing for easy identification of known impurities in a variety of deuter-ated organic solvents.However,despite the utility of Gottlieb et al.’s work,3the chemical shifts of impurities in a number of NMR solvents often used by organometallic chemists were not included.Tetrahydrofuran-d 8(THF-d 8),toluene-d 8,dichloromethane-d 2(CD 2Cl 2),chlorobenzene-d 5(C 6D 5Cl),and 2,2,2-trifluoroethanol-d 3(TFE-d 3)are com-monplace in laboratories practicing inorganic syntheses.Therefore,we have expanded the spectral data compilation with the inclusion of chemical shifts of common impurities recorded in the deuterated solvents heavily employed in our organometallic laboratories.The chemical shifts of various gases (hydrogen,methane,ethane,propane,ethylene,propylene,and carbon dioxide)often encoun-tered as reagents or products in organometallic reactions,along with organic compounds relevant to organometallic chemists (allyl acetate,benzaldehyde,carbon disulfide,carbon tetrachloride,18-crown-6,cyclohexanone,diallyl carbonate,dimethyl carbonate,dimethyl malonate,furan,Apiezon H grease,hexamethylbenzene,hexamethyldisil-oxane,imidazole,pyrrole,and pyrrolidine),have also been added to this expanded list.Experimental SectionAll deuterated solvents were obtained commercially through Cambridge Isotope Laboratories,Inc.NMR spectra were recorded at 298K using 300,500,or 600MHz spectrometers (13C{1H}NMR frequencies of 75.5,126,or 151MHz,res-pectively).Adopting the previously reported strategy,2standard solutions of mixtures of specific impurities were used to reduce the number of necessary individual NMR experiments.The combinations of organic compounds were chosen in a way in which intermolecular interactions and resonance convolution would be minimized.Unless otherwise stated,the standard solutions were prepared with qualitatively equal molar amounts of the following compounds:(solution 1)acetone,dimethylform-amide,ethanol,toluene;(solution 2)benzene,dimethyl sulf-oxide,ethyl acetate,methanol;(solution 3)acetic acid,chloro-form,diethyl ether,2-propanol,tetrahydrofuran;(solution 4)acetonitrile,dichloromethane,1,4-dioxane,n -hexane,hexa-methylphosphoramide (HMPA);(solution 5)1,2-dichloroethane,n -pentane,pyridine,hexamethylbenzene;(solution 6)tert -butyl alcohol,2,6-di-tert -butyl-4-methylphenol (BHT),cyclohexane,*To whom correspondence should be addressed.E-mail:fulmerg@.(1)For general information on 1H and 13C{1H}NMR spectroscopy,see:Balc ı,M.Basic 1H-and 13C-NMR Spectroscopy ;Elsevier:Amsterdam,2005.(2)Gottlieb,H.E.;Kotlyar,V.;Nudelman,.Chem.1997,62,7512.(3)According to ACS Publications as of December 2009(/),Gottlieb et al.’s publication 2is the most downloaded Journal of Organic Chemistry article over the preceding 12months.B Organometallics,Vol.XXX,No.XX,XXXX Fulmer et al.Table1.1H NMR Data aproton mult THF-d8CD2Cl2CDCl3toluene-d8C6D6C6D5Cl(CD3)2CO(CD3)2SO CD3CN TFE-d3CD3OD D2Osolvent residual signals 1.72 5.327.26 2.087.16 6.96 2.05 2.50 1.94 5.02 3.31 4.79 3.58 6.97 6.99 3.887.017.147.09water OH s 2.46 1.52 1.560.430.40 1.03 2.84b 3.33b 2.13 3.66 4.87acetic acid CH3s 1.89 2.06 2.10 1.57 1.52 1.76 1.96 1.91 1.96 2.06 1.99 2.08 acetone CH3s 2.05 2.12 2.17 1.57 1.55 1.77 2.09 2.09 2.08 2.19 2.15 2.22 acetonitrile CH3s 1.95 1.97 2.100.690.58 1.21 2.05 2.07 1.96 1.95 2.03 2.06 benzene CH s7.317.357.367.127.157.207.367.377.377.367.33tert-butyl alcohol CH3s 1.15 1.24 1.28 1.03 1.05 1.12 1.18 1.11 1.16 1.28 1.40 1.24 OH s c 3.160.580.63 1.30 4.19 2.18 2.20chloroform CH s7.897.327.26 6.10 6.15 6.748.028.327.587.337.9018-crown-6CH2s 3.57 3.59 3.67 3.36 3.39 3.41 3.59 3.51 3.51 3.64 3.64 3.80 cyclohexane CH2s 1.44 1.44 1.43 1.40 1.40 1.37 1.43 1.40 1.44 1.47 1.451,2-dichloroethane CH2s 3.77 3.76 3.73 2.91 2.90 3.26 3.87 3.90 3.81 3.71 3.78 dichloromethane CH2s 5.51 5.33 5.30 4.32 4.27 4.77 5.63 5.76 5.44 5.24 5.49diethyl ether CH3t,7 1.12 1.15 1.21 1.10 1.11 1.10 1.11 1.09 1.12 1.20 1.18 1.17 CH2q,7 3.38 3.43 3.48 3.25 3.26 3.31 3.41 3.38 3.42 3.58 3.49 3.56 diglyme CH2m 3.43 3.57 3.65 3.43 3.46 3.49 3.56 3.51 3.53 3.67 3.61 3.67 CH2m 3.53 3.50 3.57 3.31 3.34 3.37 3.47 3.38 3.45 3.62 3.58 3.61OCH3s 3.28 3.33 3.39 3.12 3.11 3.16 3.28 3.24 3.29 3.41 3.35 3.37 dimethylformamide CH s7.917.968.027.577.637.737.967.957.927.867.977.92 CH3s 2.88 2.91 2.96 2.37 2.36 2.51 2.94 2.89 2.89 2.98 2.99 3.01CH3s 2.76 2.82 2.88 1.96 1.86 2.30 2.78 2.73 2.77 2.88 2.86 2.85 1,4-dioxane CH2s 3.56 3.65 3.71 3.33 3.35 3.45 3.59 3.57 3.60 3.76 3.66 3.75 DME CH3s 3.28 3.34 3.40 3.12 3.12 3.17 3.28 3.24 3.28 3.40 3.35 3.37 CH2s 3.43 3.49 3.55 3.31 3.33 3.37 3.46 3.43 3.45 3.61 3.52 3.60 ethane CH3s0.850.850.870.810.800.790.830.820.850.850.850.82 ethanol CH3t,7 1.10 1.19 1.250.970.96 1.06 1.12 1.06 1.12 1.22 1.19 1.17 CH2q,7d 3.51 3.66 3.72 3.36 3.34 3.51 3.57 3.44 3.54 3.71 3.60 3.65OH s c,d 3.30 1.33 1.320.830.50 1.39 3.39 4.63 2.47ethyl acetate CH3CO s 1.94 2.00 2.05 1.69 1.65 1.78 1.97 1.99 1.97 2.03 2.01 2.07C H2CH3q,7 4.04 4.08 4.12 3.87 3.89 3.96 4.05 4.03 4.06 4.14 4.09 4.14CH2C H3t,7 1.19 1.23 1.260.940.92 1.04 1.20 1.17 1.20 1.26 1.24 1.24 ethylene CH2s 5.36 5.40 5.40 5.25 5.25 5.29 5.38 5.41 5.41 5.40 5.39 5.44 ethylene glycol CH2s e 3.48 3.66 3.76 3.36 3.41 3.58 3.28 3.34 3.51 3.72 3.59 3.65 H grease f CH3m0.85-0.910.84-0.900.84-0.870.89-0.960.90-0.980.86-0.920.900.82-0.880.88-0.940.86-0.93CH2br s 1.29 1.27 1.25 1.33 1.32 1.30 1.29 1.24 1.33 1.29 hexamethylbenzene CH3s 2.18 2.20 2.24 2.10 2.13 2.10 2.17 2.14 2.19 2.24 2.19n-hexane CH3t,70.890.890.880.880.890.850.880.860.890.910.90 CH2m 1.29 1.27 1.26 1.22 1.24 1.19 1.28 1.25 1.28 1.31 1.29 HMDSO CH3s0.070.070.070.100.120.100.070.060.070.080.070.28 HMPA CH3d,9.5 2.58 2.60 2.65 2.42 2.40 2.47 2.59 2.53 2.57 2.63 2.64 2.61 hydrogen H2s 4.55 4.59 4.62 4.50 4.47 4.49 4.54 4.61 4.57 4.53 4.56 imidazole CH(2)s7.487.637.677.307.337.537.627.637.577.617.677.78 CH(4,5)s 6.947.077.10 6.86 6.907.017.047.017.017.037.057.14 methane CH4s0.190.210.220.170.160.150.170.200.200.180.200.18 methanol CH3s g 3.27 3.42 3.49 3.03 3.07 3.25 3.31 3.16 3.28 3.44 3.34 3.34 OH s c,g 3.02 1.09 1.09 1.30 3.12 4.01 2.16nitromethane CH3s 4.31 4.31 4.33 3.01 2.94 3.59 4.43 4.42 4.31 4.28 4.34 4.40 n-pentane CH3t,70.890.890.880.870.870.840.880.860.890.900.90 CH2m 1.31 1.30 1.27 1.25 1.23 1.23 1.27 1.27 1.29 1.33 1.29 propane CH3t,7.30.900.900.900.890.860.840.880.870.900.900.910.88 CH2sept,7.3 1.33 1.32 1.32 1.32 1.26 1.26 1.31 1.29 1.33 1.33 1.34 1.30 2-propanol CH3d,6 1.08 1.17 1.220.950.95 1.04 1.10 1.04 1.09 1.20 1.50 1.17 CH sept,6 3.82 3.97 4.04 3.65 3.67 3.82 3.90 3.78 3.87 4.05 3.92 4.02 propylene CH3dt,6.4,1.5 1.69 1.71 1.73 1.55 1.55 1.58 1.68 1.68 1.70 1.70 1.70 1.70 CH2(1)dm,10 4.89 4.93 4.94 4.92 4.95 4.91 4.90 4.94 4.93 4.93 4.91 4.95CH2(2)dm,17 4.99 5.03 5.03 4.98 5.01 4.98 5.00 5.03 5.04 5.03 5.01 5.06CH m 5.79 5.84 5.83 5.70 5.72 5.72 5.81 5.80 5.85 5.87 5.82 5.90 pyridine CH(2,6)m8.548.598.628.478.538.518.588.588.578.458.538.52 CH(3,5)m7.257.287.29 6.67 6.66 6.907.357.397.337.407.447.45CH(4)m7.657.687.68 6.99 6.987.257.767.797.737.827.857.87 pyrrole NH br t9.968.698.407.717.808.6110.0210.759.27CH(2,5)m 6.66 6.79 6.83 6.43 6.48 6.62 6.77 6.73 6.75 6.84 6.72 6.93CH(3,4)m 6.02 6.19 6.26 6.27 6.37 6.27 6.07 6.01 6.10 6.24 6.08 6.26 pyrrolidine h CH2(2,5)m 2.75 2.82 2.87 2.54 2.54 2.64 2.67 2.75 3.11 2.80 3.07 CH2(3,4)m 1.59 1.67 1.68 1.36 1.33 1.43 1.55 1.61 1.93 1.72 1.87 silicone grease CH3s0.110.090.070.260.290.140.13-0.060.080.160.10 tetrahydrofuran CH2(2,5)m 3.62 3.69 3.76 3.54 3.57 3.59 3.63 3.60 3.64 3.78 3.71 3.74 CH2(3,4)m 1.79 1.82 1.85 1.43 1.40 1.55 1.79 1.76 1.80 1.91 1.87 1.88 toluene CH3s 2.31 2.34 2.36 2.11 2.11 2.16 2.32 2.30 2.33 2.33 2.32 CH(2,4,6)m7.107.157.17 6.96-7.017.027.01-7.087.10-7.207.187.10-7.307.10-7.307.16CH(3,5)m7.197.247.257.097.137.10-7.177.10-7.207.257.10-7.307.10-7.307.16 triethylamine CH3t,70.970.99 1.030.950.960.930.960.930.96 1.31 1.050.99 CH2q,7 2.46 2.48 2.53 2.39 2.40 2.39 2.45 2.43 2.45 3.12 2.58 2.57a Except for the compounds in solutions8-10,as well as the gas samples,hexamethylbenzene,and the corrected values mentioned in the Supporting Information,all data for the solvents CDCl3,C6D6,(CD3)2CO,(CD3)2SO,CD3CN,CD3OD,and D2O were previously reported in ref2.b A signal for HDO is also observed in(CD3)2SO(3.30ppm)and(CD3)2CO(2.81ppm),often seen as a1:1:1triplet(2J H,D=1Hz).c Not all OH signals were observable.d In some solvents,the coupling interaction between the CH2and the OH protons may be observed(J=5Hz).e In CD3CN,the OH proton was seen as a multiplet at2.69ppm,as well as extra coupling to the CH2resonance.f Apiezon brand H grease.g In some solvents,a coupling interaction between the CH3and the OH protons may be observed(J=5.5Hz).h Pyrrolidine was observed to react with(CD3)2CO.Article Organometallics,Vol.XXX,No.XX,XXXX CTable2.13C{1H}NMR Data acarbon THF-d8CD2Cl2CDCl3toluene-d8C6D6C6D5Cl(CD3)2CO(CD3)2SO CD3CN TFE-d3CD3OD D2O solvent signals67.2153.8477.16137.48128.06134.1929.8439.52 1.3261.5049.0025.31128.87129.26206.26118.26126.28127.96128.25125.13125.9620.43acetic acid CO171.69175.85175.99175.30175.82175.67172.31171.93173.21177.96175.11177.21 CH320.1320.9120.8120.2720.3720.4020.5120.9520.7320.9120.5621.03acetone CO204.19206.78207.07204.00204.43204.83205.87206.31207.4332.35209.67215.94 CH330.1731.0030.9230.0330.1430.1230.6030.5630.91214.9830.6730.89acetonitrile CN116.79116.92116.43115.76116.02115.93117.60117.91118.26118.95118.06119.68 CH30.45 2.03 1.890.030.200.63 1.12 1.03 1.79 1.000.85 1.47 benzene CH128.84128.68128.37128.57128.62128.38129.15128.30129.32129.84129.34tert-butyl alcohol(CH3)3C67.5069.1169.1568.1268.1968.1968.1366.8868.7472.3569.4070.36(C H3)3C30.5731.4631.2530.4930.4731.1330.7230.3830.6831.0730.9130.29carbon dioxide CO2125.69125.26124.99124.86124.76126.08125.81124.21125.89126.92126.31carbon disulfide CS2193.37192.95192.83192.71192.69192.49193.58192.63193.60196.26193.82197.25carbon tetrachloride CCl496.8996.5296.3496.5796.4496.3896.6595.4496.6897.7497.2196.73 chloroform CH79.2477.9977.3677.8977.7977.6779.1979.1679.1778.8379.4418-crown-6CH271.3470.4770.5570.8670.5970.5571.2569.8571.2270.8071.4770.14cyclohexane CH227.5827.3826.9427.3127.2326.9927.5126.3327.6328.3427.961,2-dichloroethane CH244.6444.3543.5043.4043.5943.6045.2545.0245.5445.2845.11dichloromethane CH254.6754.2453.5253.4753.4653.5454.9554.8455.3254.4654.78diethyl ether CH315.4915.4415.2015.4715.4615.3515.7815.1215.6315.3315.4614.77CH266.1466.1165.9165.9465.9465.7966.1262.0566.3267.5566.8866.42 diglyme CH358.7258.9559.0158.6258.6658.4258.7757.9858.9059.4059.0658.67CH271.1770.7070.5170.9270.8770.5671.0369.5470.9973.0571.3370.05CH272.7272.2571.9072.3972.3572.0772.6371.2572.6371.3372.9271.63 dimethylformamide CH161.96162.57162.62161.93162.13162.01162.79162.29163.31166.01164.73165.53CH335.6536.5636.5035.2235.2535.4536.1535.7336.5737.7636.8937.54CH330.7031.3931.4530.6430.7230.7131.0330.7331.3230.9631.6132.031,4-dioxane CH267.6567.4767.1467.1767.1666.9567.6066.3667.7268.5268.1167.19 DME CH358.7259.0259.0858.6358.6858.3158.4558.0358.8959.5259.0658.67CH272.5872.2471.8472.2572.2171.8172.4771.1772.4772.8772.7271.49 ethane CH3 6.79 6.91 6.89 6.94 6.96 6.91 6.88 6.61 6.997.01 6.98ethanol CH318.9018.6918.4118.7818.7218.5518.8918.5118.8018.1118.4017.47CH257.6058.5758.2857.8157.8657.6357.7256.0757.9659.6858.2658.05 ethyl acetate C H3CO20.4521.1521.0420.4620.5620.5020.8320.6821.1621.1820.8821.15CO170.32171.24171.36170.02170.44170.20170.96170.31171.68175.55172.89175.26CH260.3060.6360.4960.0860.2160.0660.5659.7460.9862.7061.5062.32CH314.3714.3714.1914.2314.1914.0714.5014.4014.5414.3614.4913.92 ethylene CH2123.09123.20123.13122.92122.96122.95123.47123.52123.69124.08123.46 ethylene glycol CH264.3564.0863.7964.2964.3464.0364.2662.7664.2264.8764.3063.17H grease b CH230.4530.1429.7130.3130.2230.11hexamethylbenzene C131.88132.09132.21131.72131.79131.54132.22131.10132.61134.04132.53CH316.7116.9316.9816.8416.9516.6816.8616.6016.9417.0416.90n-hexane CH314.2214.2814.1414.3414.3214.1814.3413.8814.4314.6314.45CH2(2,5)23.3323.0722.7023.1223.0422.8623.2822.0523.4024.0623.68CH2(3,4)32.3432.0131.6432.0631.9631.7732.3030.9532.3633.1732.73HMDSO CH3 1.83 1.96 1.97 1.99 2.05 1.92 2.01 1.96 2.07 2.09 1.99 2.31 HMPA c CH336.8936.9936.8736.8036.8836.6437.0436.4237.1037.2137.0036.46 imidazole CH(2)135.72135.76135.38135.57135.76135.50135.89135.15136.33136.58136.31136.65CH(4,5)122.20122.16122.00122.13122.16121.96122.31121.55122.78122.93122.60122.43 methane CH4-4.90-4.33-4.63-4.34-4.29-4.33-5.33-4.01-4.61-5.88-4.90 methanol CH349.6450.4550.4149.9049.9749.6649.7748.5949.9050.6749.8649.50d nitromethane CH362.4963.0362.5061.1461.1661.6863.2163.2863.6663.1763.0863.22n-pentane CH314.1814.2414.0814.2714.2514.1014.2913.2814.3714.5414.39 CH2(2,4)23.0022.7722.3822.7922.7222.5422.9821.7023.0823.7523.38CH2(3)34.8734.5734.1634.5434.4534.2634.8333.4834.8935.7635.30propane CH316.6016.6316.6316.6516.6616.5616.6816.3416.7316.9316.80 CH216.8216.6316.3716.6316.6016.4816.7815.6716.9117.4617.192-propanol CH325.7025.4325.1425.2425.1825.1425.6725.4325.5525.2125.2724.38 CH66.1464.6764.5064.1264.2364.1863.8564.9264.3066.6964.7164.88 propylene CH319.2719.4719.5019.3219.3819.3219.4219.2019.4819.6319.50 CH2115.74115.70115.74115.89115.92115.86116.03116.07116.12116.38116.04CH134.02134.21133.91133.61133.69133.57134.34133.55134.78136.00134.61pyridine CH(2,6)150.57150.27149.90150.25150.27149.93150.67149.58150.76149.76150.07149.18 CH(3,5)124.08124.06123.75123.46123.58123.49124.57123.84127.76126.27125.53125.12CH(4)135.99136.16135.96135.17135.28135.32136.56136.05136.89139.62138.35138.27 pyrrole CH(2,5)118.03117.93117.77117.61117.78117.65117.98117.32118.47119.61118.28119.06 CH(3,4)107.74108.02107.98108.15108.21108.03108.04107.07108.31108.85108.11107.83 pyrrolidine e CH2(2,5)45.8247.0246.9347.1246.8646.7546.5147.5747.4347.2346.83 CH2(3,4)26.1725.8325.5625.7525.6525.5925.2626.3425.7326.2925.86 silicone grease CH3 1.20 1.22 1.19 1.37 1.38 1.09 1.40 2.87 2.10 tetrahydrofuran CH2(2,5)68.0368.1667.9767.7567.8067.6468.0767.0368.3369.5368.8368.68 CH2(3,4)26.1925.9825.6225.7925.7225.6826.1525.1426.2726.6926.4825.67 toluene CH321.2921.5321.4621.3721.1021.2321.4620.9921.5021.6221.50 C(1)138.24138.36137.89137.84137.91137.65138.48137.35138.90139.92138.85CH(2,6)129.47129.35129.07129.33129.33129.12129.76128.88129.94130.58129.91CH(3,5)128.71128.54128.26128.51128.56128.31129.03128.18129.23129.79129.20CH(4)125.84125.62125.33125.66125.68125.43126.12125.29126.28126.82126.29 triethylamine CH312.5112.1211.6112.3912.3511.8712.4911.7412.389.5111.099.07 CH247.1846.7546.2546.8246.7746.3647.0745.7447.1048.4546.9647.19a Except for the compounds in solutions8-10,as well as the gas samples,hexamethylbenzene,and the corrected values mentioned in the Supporting Information,all data for the solvents CDCl3,C6D6,(CD3)2CO,(CD3)2SO,CD3CN,CD3OD,and D2O were previously reported in ref2.b Apiezon c2d eD Organometallics,Vol.XXX,No.XX,XXXX Fulmer et al.1,2-dimethoxyethane(DME),nitromethane,poly(dimethylsiloxane) (silicone grease),triethylamine;(solution7)diglyme,dimethyl-acetamide,ethylene glycol,ethyl methyl ketone;(solution8) allyl acetate,2,6-di-tert-butyl-4-methoxyphenol(BHA),long-chain,linear aliphatic hydrocarbons from pump oil;4(solu-tion9)benzaldehyde,carbon disulfide,carbon tetrachloride, cyclohexanone,dimethyl malonate,furan,Apiezon H grease (H grease);(solution10)18-crown-6,diallyl carbonate,dimethyl carbonate,hexamethyldisiloxane(HMDSO),imidazole,pyrrole, pyrrolidine.5In the case of TFE-d3,nitromethane was omitted from solution6and run separately,since the protons of nitro-methane exchange with deuterium from TFE-d3in the presence of triethylamine.In the case of(CD3)2CO,pyrrolidine was omitted from solution10,since the two compounds were observed to react with each other.The gases used in this study included hydrogen,methane,ethane,propane,ethylene,propylene,and carbon dioxide.Before examining the various standard contaminant solu-tions by1H NMR spectroscopy,solvent residual signals6and chemical shifts for H2O7for each NMR solvent were refer-enced against tetramethylsilane(TMS,δ0ppm)and reported. Before collecting13C{1H}NMR spectral data,solvent signals6 were recorded with reference to the signal of a TMS internal standard.For D2O,1H NMR spectra were referenced to the methyl signal(δ0ppm)of sodium3-(trimethylsilyl)propane-sulfonate,8,9and13C{1H}NMR spectra were referenced to the signal for the methyl group of methanol(one drop,added as an internal standard),which was set to49.50ppm.2In a typical experiment for collecting1H NMR spectral data,a 3μL sample of a standard contaminant solution was added to an NMR tube containing approximately0.4mL of a deuterated solvent.For13C{1H}NMR spectral data collection,an approxi-mately50μL sample of the standard contaminant solution was added.When there was any uncertainty in the assignment of a resonance,the solution was spiked with an additional1-2μL of the impurity in question to accurately identify its chemical shift.In cases where the chemical shifts of resonances were highly dependent on the concentration of the impurities pre-sent,ambiguous resonances were instead resolved via gradient-selected heteronuclear single-quantum coherence(gs-HSQC) and gradient-selected heteronuclear multiple-quantum coherence (gs-HMQC)NMR spectroscopies.For the experiments involving gases,a J.Young NMR tube containing approximately0.4mL of NMR solvent was first degassed with three freeze-pump-thaw ing a vacuum line equipped with a gas manifold,1atm of the desired gas was added to the tube.Each gas was run separately,degassing between each gas sample.Results and DiscussionChemical shifts for each of the impurities are reported in the tables:1H and13C{1H}NMR spectral data of all sub-strates are presented in Tables1and2,respectively.Notably, physically larger tables,containing all the data from Tables1 and2as well as the chemical shifts of additional organic compounds,are provided in the Supporting Information. Unless noted otherwise,coupling constants(reported in Hz) and resonance multiplicities(abbreviated as follows:s= singlet,d=doublet,t=triplet,q=quartet,p=pentet, sept=septet,m=multiplet,br=broad)were observed to be solvent-independent.It was noted that the amount of gas dissolved in solution gave1H NMR signal integrations that were qualitatively comparable to those for the solutions made with the3μL additions of the liquid or solid contaminants.However,typi-cally in order to observe signals for the gas samples by13C{1H} NMR spectroscopy,additional time for data collection was required.The solubility of each gas in D2O was extremely limited,making13C detection impractical.Of all the gases, methane required the most number of transients in order to obtain an observable signal by13C{1H}NMR spectroscopy. In most cases,the13C chemical shift of methane was acquired through the use of gs-HMQC NMR spectroscopy to provide enhanced sensitivity.In order to reflect what would be ob-served in typical NMR-scale experiments,13C detection was not pursued with isotopically enriched gases.A number of misreported values were discovered in the years since the original publication10and in the preparation of this paper. These are detailed in the Supporting Information,and the values are now correctly listed in Tables1and2. Acknowledgment.G.R.F.and K.I.G.thank the Depart-ment of Energy(Contract No.DE-FG02-06ER15765)for support.A.J.M.M.and J.E.B.thank the Moore Founda-tion for support.N.H.S.and B.M.S.thank Abbott Labora-tories,Amgen,Merck,Bristol-Myers Squibb,Boehringer Ingelheim,the Gordon and Betty Moore Foundation,and Caltech for financial support.Supporting Information Available:Large-format tables of the all the NMR data.This material is available free of charge via the Internet at .(4)VWR brand vacuum pump oil#19.(5)The components of solution10were stable together in dilute solution but unstable when neat mixtures were prepared.In general,it was observed that the nitrogen-containing compounds and possibly 18-crown-6catalyzed the hydrolysis of the carbonates,reacted directly with them,or both.Therefore,for the purpose of storage,the solution was partitioned into two subsolutions:(solution10A)18-crown-6, imidazole,pyrrole,pyrrolidine;(solution10B)diallyl carbonate,di-methyl carbonate,hexamethyldisiloxane.These subsolutions were stable for long periods as neat mixtures and were combined to form solution10by adding equal portions to an NMR tube containing the desired deuterated solvent.(6)For1H NMR spectra,the solvent residual signals arise from the proton of isotopomers containing one less deuterium atom than the perdeuterated solvent:e.g.,CDHCl2in CD2Cl2.For13C NMR spectra, the solvent signals arise from the13C atoms at natural abundance in the perdeuterated solvent.(7)The chemical shift for H2O can vary depending on the tempera-ture,[H2O],and the solutes present:e.g.,a downfield shift may be observed in the presence of any hydrogen bond acceptors.For more information see page75of ref1.(8)Harris,R.K.;Becker,E.D.;Cabral de Menezes,S.M.;Granger, P.;Hoffman,R.E.;Zilm,K.W.Pure Appl.Chem.2008,80,59.(9)For information on the temperature dependence of HDO chemi-cal shifts in D2O,see ref2.(10)The misreported value for acetonitrile in C6D6from the original paper2was also pointed out by Dr.Jongwook Choi,to whom we are grateful.Supporting InformationNMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to theOrganometallic ChemistGregory R. Fulmer,*,1 Alexander J. M. Miller,2 Nathaniel H. Sherden,2 Hugo E. Gottlieb,3 Abraham Nudelman,3 Brian M. Stoltz,2 John E. Bercaw,2 and Karen I.Goldberg11 Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700;2 Arnold and Mabel Beckman Laboratories of Chemical Synthesis, and Caltech Center for Catalysis and Chemical Synthesis, Division of Chemistry and Chemical Engineering California Institute of Technology,Pasadena, California 91125;3 Department of Chemistry, Bar Ilan University, Ramat Gan 52900, Israel.Corrections and Comments........................................................................................................S2 1H NMR Data (Table S1)............................................................................................................S3 13C NMR Data (Table S2)...........................................................................................................S5 Individual Solvent Tables – NMR Data Sorted by Chemical Shift (Tables S3–S26)............S7 References..................................................................................................................................S19Corrections and CommentsIn the preparation of this manuscript, several errors were discovered in the original paper1and are reported herein. While comparing the 1H NMR spectral data obtained in toluene-d8 to that in C6D6, it was discovered that the 1H NMR chemical shifts for acetic acid (C H3), acetonitrile (C H3) and tert-butyl alcohol (O H) in C6D6had each been misreported at 1.55 ppm in the original paper; the values have now been correctly listed as 1.52, 0.58, and 0.63 ppm, respectively. The original paper's assignments for BHT's C(3,5) and C(4) in C6D6, (CD3)2CO, (CD3)2SO, CD3CN, and CD3OD were reversed and are now corrected. The resonances for 1,2-dimethoxyethane (C H2) in (CD3)2CO, silicone grease (C H3) in CDCl3, and 2-propanol (C H3) in CD3OD have been corrected and are reported as 72.47, 1.04, and 1.15 ppm, respectively. No other significant differences were discovered when comparing our data to that which had been previously reported; however, we have additionally provided the O H resonance for ethanol in C6D6 (0.50 ppm), the C H3 resonance for silicone grease in (CD3)2SO (–0.06 ppm), and replaced the “grease” entry (formerly motor oil1) with VWR vacuum pump oil #19, which is now reported in each deuterated solvent.Table S1.1H NMR Data2proton mult THF-d8CD2Cl2CDCl3toluene-d8C6D6C6D5Cl(CD3)2CO(CD3)2SO CD3CN TFE-d3CD3OD D2O solvent residual signals 1.72 5.327.26 2.087.16 6.96 2.05 2.50 1.94 5.02 3.31 4.793.58 6.97 6.99 3.887.017.147.09water OH s 2.46 1.52 1.560.430.40 1.03 2.843 3.333 2.13 3.66 4.87-acetic acid CH3s 1.89 2.06 2.10 1.57 1.52 1.76 1.96 1.91 1.96 2.06 1.99 2.08 acetone CH3s 2.05 2.12 2.17 1.57 1.55 1.77 2.09 2.09 2.08 2.19 2.15 2.22 acetonitrile CH3s 1.95 1.97 2.100.690.58 1.21 2.05 2.07 1.96 1.95 2.03 2.06 allyl acetate C H CH2ddt 5.90 5.92 5.93 5.674 5.684 5.77 5.92 5.91 5.93 5.93 5.94 5.99 CHC H2(1)ddt 5.27 5.31 5.32 5.05 5.06 5.15 5.29 5.29 5.29 5.32 5.30 5.37CHC H2(2)ddt 5.15 5.22 5.24 4.94 4.94 5.04 5.18 5.20 5.21 5.25 5.21 5.30 CH2ddd 4.50 4.55 4.57 4.34 4.38 4.44 4.53 4.52 4.53 4.58 4.56 4.62CH3s 1.98 2.05 2.09 1.63 1.63 1.80 2.02 2.03 2.02 2.07 2.05 2.13 benzaldehyde HCO s9.9810.0110.039.579.649.7710.0510.0210.019.8810.009.96 CH(2,6)m7.86–7.887.87–7.897.88–7.917.45–7.477.49–7.537.59–7.617.92–7.947.91–7.937.89–7.917.90–7.927.90–7.937.97–7.99CH(3,5)m7.51–7.557.53–7.577.51–7.57 6.95–6.99 6.93–6.997.15–7.197.59–7.637.61–7.677.57–7.617.56–7.597.56–7.607.57–7.66CH(4)m7.60–7.647.63–7.677.61–7.657.03–7.077.01–7.077.24–7.287.69–7.737.69–7.757.67–7.717.68–7.727.66–7.707.76–7.80 benzene CH s7.317.357.367.127.157.207.367.377.377.367.33-tert-butyl alcohol CH3s 1.15 1.24 1.28 1.03 1.05 1.12 1.18 1.11 1.16 1.28 1.40 1.24 OH s5 3.16--0.580.63 1.30- 4.19 2.18 2.20--BHA ArH s 6.68 6.73 6.76 6.83 6.93 6.83 6.72 6.62 6.73 6.87 6.71-OH s5 5.64 4.76 4.76 4.45 4.53 4.62 5.65 6.52 4.98- 4.85-ArOCH3s 3.68 3.73 3.77 3.48 3.48 3.61 3.72 3.66 3.72 3.79 3.72-ArC(CH3)3s 1.40 1.42 1.44 1.34 1.41 1.37 1.41 1.36 1.40 1.44 1.41-BHT ArH s 6.92 6.97 6.98 6.997.05 6.97 6.96 6.87 6.977.06 6.92-OH s5 5.81 5.00 5.01 4.72 4.79 5.50- 6.65 5.20---ArCH3s 2.21 2.25 2.27 2.23 2.24 2.20 2.22 2.18 2.22 2.24 2.21-ArC(CH3)3s 1.40 1.42 1.43 1.36 1.38 1.37 1.41 1.36 1.39 1.43 1.40-chloroform CH s7.897.327.26 6.10 6.15 6.748.028.327.587.337.90-18-crown-6CH2s 3.57 3.59 3.67 3.36 3.39 3.41 3.59 3.51 3.51 3.64 3.64 3.80 cyclohexane CH2s 1.44 1.44 1.43 1.40 1.40 1.37 1.43 1.40 1.44 1.47 1.45-cyclohexanone CH2(2,6)t 2.24 2.29 2.33 1.95 1.98 2.08 2.27 2.25 2.27 2.38 2.34 2.40 CH2(3,5)m 1.77–1.82 1.81–1.87 1.84–1.86 1.33–1.39 1.28–1.37 1.48–1.53 1.79–1.83 1.74–1.78 1.79–1.84 1.87–1.92 1.85–1.87 1.85–1.90CH2(4)m 1.68–1.71 1.69–1.72 1.71–1.73 1.16–1.20 1.08–1.16 1.33–1.37 1.70–1.74 1.64–1.66 1.67–1.72 1.75–1.78 1.74–1.76 1.70–1.75 diallyl carbonate C H CH2ddt 5.92 5.95 5.94 5.63 5.65 5.75 5.96 5.93 5.96 5.92 5.94 5.99 CHC H2(1)ddt 5.31 5.35 5.37 5.09 5.09 5.17 5.35 5.33 5.34 5.35 5.34 5.40CHC H2(2)ddt 5.19 5.26 5.27 4.92 4.92 5.03 5.23 5.25 5.25 5.28 5.25 5.32 CH2ddd 4.58 4.61 4.64 4.34 4.38 4.46 4.62 4.61 4.61 4.62 4.61 4.69 1,2-dichloroethane CH2s 3.77 3.76 3.73 2.91 2.90 3.26 3.87 3.90 3.81 3.71 3.78-dichloromethane CH2s 5.51 5.33 5.30 4.32 4.27 4.77 5.63 5.76 5.44 5.24 5.49-diethyl ether CH3t, 7 1.12 1.15 1.21 1.10 1.11 1.10 1.11 1.09 1.12 1.20 1.18 1.17 CH2q, 7 3.38 3.43 3.48 3.25 3.26 3.31 3.41 3.38 3.42 3.58 3.49 3.56 diglyme CH2m 3.43 3.57 3.65 3.43 3.46 3.49 3.56 3.51 3.53 3.67 3.61 3.67 CH2m 3.53 3.50 3.57 3.31 3.34 3.37 3.47 3.38 3.45 3.62 3.58 3.61OCH3s 3.28 3.33 3.39 3.12 3.11 3.16 3.28 3.24 3.29 3.41 3.35 3.37 1,2-dimethoxyethane CH3s 3.28 3.34 3.40 3.12 3.12 3.17 3.28 3.24 3.28 3.40 3.35 3.37 CH2s 3.43 3.49 3.55 3.31 3.33 3.37 3.46 3.43 3.45 3.61 3.52 3.60 dimethylacetamide CH3CO s 1.94 2.02 2.09 1.59 1.60 1.74 1.97 1.96 1.97 2.09 2.07 2.08 NCH3s 2.95 2.97 3.02 2.56 2.57 2.65 3.00 2.94 2.96 3.05 3.31 3.06NCH3s 2.82 2.87 2.94 2.11 2.05 2.42 2.83 2.78 2.83 2.94 2.92 2.90 dimethyl carbonate CH3s 3.69 3.75 3.79 3.31 3.30 3.48 3.72 3.69 3.72 3.77 3.74 3.69 dimethyl malonate CH3s 3.65 3.72 3.75 3.24 3.23 3.41 3.68 3.65 3.68 3.76 3.72 3.78 CH2s 3.35 3.37 3.40 2.92 2.97 3.15 3.42 3.53 3.38 3.41 3.44 3.60 dimethylformamide CH s7.917.968.027.577.637.737.967.957.927.867.977.92 CH3s 2.88 2.91 2.96 2.37 2.36 2.51 2.94 2.89 2.89 2.98 2.99 3.01CH3s 2.76 2.82 2.88 1.96 1.86 2.30 2.78 2.73 2.77 2.88 2.86 2.85 dimethyl sulfoxide CH3s 2.45 2.55 2.62 1.64 1.68 2.03 2.52 2.54 2.50 2.63 2.65 2.71 1,4-dioxane CH2s 3.56 3.65 3.71 3.33 3.35 3.45 3.59 3.57 3.60 3.76 3.66 3.75 ethane CH3s0.850.850.870.810.800.790.830.820.850.850.850.82 ethanol CH3t, 7 1.10 1.19 1.250.970.96 1.06 1.12 1.06 1.12 1.22 1.19 1.17 CH2q, 76 3.51 3.66 3.72 3.36 3.34 3.51 3.57 3.44 3.54 3.71 3.60 3.65OH s5,6 3.30 1.33 1.320.830.50 1.39 3.39 4.63 2.47---ethyl acetate CH3CO s 1.94 2.00 2.05 1.69 1.65 1.78 1.97 1.99 1.97 2.03 2.01 2.07C H2CH3q, 7 4.04 4.08 4.12 3.87 3.89 3.96 4.05 4.03 4.06 4.14 4.09 4.14CH2C H3t, 7 1.19 1.23 1.260.940.92 1.04 1.20 1.17 1.20 1.26 1.24 1.24 ethyl methyl ketone CH3CO s 2.03 2.09 2.14 1.59 1.58 1.78 2.07 2.07 2.06 2.16 2.12 2.19C H2CH3q, 7 2.39 2.43 2.46 1.82 1.81 2.06 2.45 2.43 2.43 2.49 2.50 3.18CH2C H3t, 70.96 1.00 1.060.840.850.890.960.910.96 1.05 1.01 1.26 ethylene CH2s 5.36 5.40 5.40 5.25 5.25 5.29 5.38 5.41 5.41 5.40 5.39 5.44 ethylene glycol CH2s7 3.48 3.66 3.76 3.36 3.41 3.58 3.28 3.34 3.51 3.72 3.59 3.65 furan CH(2,5)dd7.487.467.457.107.137.247.567.677.527.447.497.57 CH(3,4)dd 6.37 6.41 6.40 6.07 6.08 6.19 6.43 6.47 6.44 6.42 6.40 6.51H grease8CH3m0.85–0.910.84–0.900.84–0.870.89–0.960.90–0.980.86–0.920.900.82–0.88-0.88–0.940.86–0.93-CH2br s 1.29 1.27 1.25 1.33 1.32 1.30 1.29 1.24- 1.33 1.29-hexamethylbenzene CH3s 2.18 2.20 2.24 2.10 2.13 2.10 2.17 2.14 2.19 2.24 2.19-hexamethyldisiloxane CH3s0.070.070.070.100.120.100.070.060.070.080.070.28。

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Organometallics XXXX,XXX,000–000ADOI:10.1021/om100106eNMR Chemical Shifts of Trace Impurities:Common Laboratory Solvents,Organics,and Gases in DeuteratedSolvents Relevant to the OrganometallicChemistGregory R.Fulmer,*,†Alexander ler,‡Nathaniel H.Sherden,‡Hugo E.Gottlieb,§Abraham Nudelman,§Brian M.Stoltz,‡John E.Bercaw,‡andKaren I.Goldberg ††Department of Chemistry,University of Washington,Box 351700,Seattle,Washington 98195-1700,‡Arnold and Mabel Beckman Laboratories of Chemical Synthesis and Caltech Center for Catalysis andChemical Synthesis,Division of Chemistry and Chemical Engineering,California Institute of Technology,Pasadena,California 91125,and §Department of Chemistry,Bar Ilan University,Ramat Gan 52900,IsraelReceived February 11,2010Tables of 1H and 13C NMR chemical shifts have been compiled for common organic compounds often used as reagents or found as products or contaminants in deuterated organic solvents.Building upon the work of Gottlieb,Kotlyar,and Nudelman in the Journal of Organic Chemistry,signals for common impurities are now reported in additional NMR solvents (tetrahydrofuran-d 8,toluene-d 8,dichloromethane-d 2,chlorobenzene-d 5,and 2,2,2-trifluoroethanol-d 3)which are frequently used in organometallic laboratories.Chemical shifts for other organics which are often used as reagents or internal standards or are found as products in organometallic chemistry are also reported for all the listed solvents.Hanging above the desk of most every chemist whose work relies heavily on using NMR spectroscopy 1is NMR Chemi-cal Shifts of Common Laboratory Solvents as Trace Impu-rities by Gottlieb,Kotlyar,and Nudelman.2By compiling the chemical shifts of a large number of contaminants commonly encountered in synthetic chemistry,the publica-tion has become an essential reference,allowing for easy identification of known impurities in a variety of deuter-ated organic solvents.However,despite the utility of Gottlieb et al.’s work,3the chemical shifts of impurities in a number of NMR solvents often used by organometallic chemists were not included.Tetrahydrofuran-d 8(THF-d 8),toluene-d 8,dichloromethane-d 2(CD 2Cl 2),chlorobenzene-d 5(C 6D 5Cl),and 2,2,2-trifluoroethanol-d 3(TFE-d 3)are com-monplace in laboratories practicing inorganic syntheses.Therefore,we have expanded the spectral data compilation with the inclusion of chemical shifts of common impurities recorded in the deuterated solvents heavily employed in our organometallic laboratories.The chemical shifts of various gases (hydrogen,methane,ethane,propane,ethylene,propylene,and carbon dioxide)often encoun-tered as reagents or products in organometallic reactions,along with organic compounds relevant to organometallic chemists (allyl acetate,benzaldehyde,carbon disulfide,carbon tetrachloride,18-crown-6,cyclohexanone,diallyl carbonate,dimethyl carbonate,dimethyl malonate,furan,Apiezon H grease,hexamethylbenzene,hexamethyldisil-oxane,imidazole,pyrrole,and pyrrolidine),have also been added to this expanded list.Experimental SectionAll deuterated solvents were obtained commercially through Cambridge Isotope Laboratories,Inc.NMR spectra were recorded at 298K using 300,500,or 600MHz spectrometers (13C{1H}NMR frequencies of 75.5,126,or 151MHz,res-pectively).Adopting the previously reported strategy,2standard solutions of mixtures of specific impurities were used to reduce the number of necessary individual NMR experiments.The combinations of organic compounds were chosen in a way in which intermolecular interactions and resonance convolution would be minimized.Unless otherwise stated,the standard solutions were prepared with qualitatively equal molar amounts of the following compounds:(solution 1)acetone,dimethylform-amide,ethanol,toluene;(solution 2)benzene,dimethyl sulf-oxide,ethyl acetate,methanol;(solution 3)acetic acid,chloro-form,diethyl ether,2-propanol,tetrahydrofuran;(solution 4)acetonitrile,dichloromethane,1,4-dioxane,n -hexane,hexa-methylphosphoramide (HMPA);(solution 5)1,2-dichloroethane,n -pentane,pyridine,hexamethylbenzene;(solution 6)tert -butyl alcohol,2,6-di-tert -butyl-4-methylphenol (BHT),cyclohexane,*To whom correspondence should be addressed.E-mail:fulmerg@.(1)For general information on 1H and 13C{1H}NMR spectroscopy,see:Balc ı,M.Basic 1H-and 13C-NMR Spectroscopy ;Elsevier:Amsterdam,2005.(2)Gottlieb,H.E.;Kotlyar,V.;Nudelman,.Chem.1997,62,7512.(3)According to ACS Publications as of December 2009(/),Gottlieb et al.’s publication 2is the most downloaded Journal of Organic Chemistry article over the preceding 12months.B Organometallics,Vol.XXX,No.XX,XXXX Fulmer et al.Table1.1H NMR Data aproton mult THF-d8CD2Cl2CDCl3toluene-d8C6D6C6D5Cl(CD3)2CO(CD3)2SO CD3CN TFE-d3CD3OD D2Osolvent residual signals 1.72 5.327.26 2.087.16 6.96 2.05 2.50 1.94 5.02 3.31 4.79 3.58 6.97 6.99 3.887.017.147.09water OH s 2.46 1.52 1.560.430.40 1.03 2.84b 3.33b 2.13 3.66 4.87acetic acid CH3s 1.89 2.06 2.10 1.57 1.52 1.76 1.96 1.91 1.96 2.06 1.99 2.08 acetone CH3s 2.05 2.12 2.17 1.57 1.55 1.77 2.09 2.09 2.08 2.19 2.15 2.22 acetonitrile CH3s 1.95 1.97 2.100.690.58 1.21 2.05 2.07 1.96 1.95 2.03 2.06 benzene CH s7.317.357.367.127.157.207.367.377.377.367.33tert-butyl alcohol CH3s 1.15 1.24 1.28 1.03 1.05 1.12 1.18 1.11 1.16 1.28 1.40 1.24 OH s c 3.160.580.63 1.30 4.19 2.18 2.20chloroform CH s7.897.327.26 6.10 6.15 6.748.028.327.587.337.9018-crown-6CH2s 3.57 3.59 3.67 3.36 3.39 3.41 3.59 3.51 3.51 3.64 3.64 3.80 cyclohexane CH2s 1.44 1.44 1.43 1.40 1.40 1.37 1.43 1.40 1.44 1.47 1.451,2-dichloroethane CH2s 3.77 3.76 3.73 2.91 2.90 3.26 3.87 3.90 3.81 3.71 3.78 dichloromethane CH2s 5.51 5.33 5.30 4.32 4.27 4.77 5.63 5.76 5.44 5.24 5.49diethyl ether CH3t,7 1.12 1.15 1.21 1.10 1.11 1.10 1.11 1.09 1.12 1.20 1.18 1.17 CH2q,7 3.38 3.43 3.48 3.25 3.26 3.31 3.41 3.38 3.42 3.58 3.49 3.56 diglyme CH2m 3.43 3.57 3.65 3.43 3.46 3.49 3.56 3.51 3.53 3.67 3.61 3.67 CH2m 3.53 3.50 3.57 3.31 3.34 3.37 3.47 3.38 3.45 3.62 3.58 3.61OCH3s 3.28 3.33 3.39 3.12 3.11 3.16 3.28 3.24 3.29 3.41 3.35 3.37 dimethylformamide CH s7.917.968.027.577.637.737.967.957.927.867.977.92 CH3s 2.88 2.91 2.96 2.37 2.36 2.51 2.94 2.89 2.89 2.98 2.99 3.01CH3s 2.76 2.82 2.88 1.96 1.86 2.30 2.78 2.73 2.77 2.88 2.86 2.85 1,4-dioxane CH2s 3.56 3.65 3.71 3.33 3.35 3.45 3.59 3.57 3.60 3.76 3.66 3.75 DME CH3s 3.28 3.34 3.40 3.12 3.12 3.17 3.28 3.24 3.28 3.40 3.35 3.37 CH2s 3.43 3.49 3.55 3.31 3.33 3.37 3.46 3.43 3.45 3.61 3.52 3.60 ethane CH3s0.850.850.870.810.800.790.830.820.850.850.850.82 ethanol CH3t,7 1.10 1.19 1.250.970.96 1.06 1.12 1.06 1.12 1.22 1.19 1.17 CH2q,7d 3.51 3.66 3.72 3.36 3.34 3.51 3.57 3.44 3.54 3.71 3.60 3.65OH s c,d 3.30 1.33 1.320.830.50 1.39 3.39 4.63 2.47ethyl acetate CH3CO s 1.94 2.00 2.05 1.69 1.65 1.78 1.97 1.99 1.97 2.03 2.01 2.07C H2CH3q,7 4.04 4.08 4.12 3.87 3.89 3.96 4.05 4.03 4.06 4.14 4.09 4.14CH2C H3t,7 1.19 1.23 1.260.940.92 1.04 1.20 1.17 1.20 1.26 1.24 1.24 ethylene CH2s 5.36 5.40 5.40 5.25 5.25 5.29 5.38 5.41 5.41 5.40 5.39 5.44 ethylene glycol CH2s e 3.48 3.66 3.76 3.36 3.41 3.58 3.28 3.34 3.51 3.72 3.59 3.65 H grease f CH3m0.85-0.910.84-0.900.84-0.870.89-0.960.90-0.980.86-0.920.900.82-0.880.88-0.940.86-0.93CH2br s 1.29 1.27 1.25 1.33 1.32 1.30 1.29 1.24 1.33 1.29 hexamethylbenzene CH3s 2.18 2.20 2.24 2.10 2.13 2.10 2.17 2.14 2.19 2.24 2.19n-hexane CH3t,70.890.890.880.880.890.850.880.860.890.910.90 CH2m 1.29 1.27 1.26 1.22 1.24 1.19 1.28 1.25 1.28 1.31 1.29 HMDSO CH3s0.070.070.070.100.120.100.070.060.070.080.070.28 HMPA CH3d,9.5 2.58 2.60 2.65 2.42 2.40 2.47 2.59 2.53 2.57 2.63 2.64 2.61 hydrogen H2s 4.55 4.59 4.62 4.50 4.47 4.49 4.54 4.61 4.57 4.53 4.56 imidazole CH(2)s7.487.637.677.307.337.537.627.637.577.617.677.78 CH(4,5)s 6.947.077.10 6.86 6.907.017.047.017.017.037.057.14 methane CH4s0.190.210.220.170.160.150.170.200.200.180.200.18 methanol CH3s g 3.27 3.42 3.49 3.03 3.07 3.25 3.31 3.16 3.28 3.44 3.34 3.34 OH s c,g 3.02 1.09 1.09 1.30 3.12 4.01 2.16nitromethane CH3s 4.31 4.31 4.33 3.01 2.94 3.59 4.43 4.42 4.31 4.28 4.34 4.40 n-pentane CH3t,70.890.890.880.870.870.840.880.860.890.900.90 CH2m 1.31 1.30 1.27 1.25 1.23 1.23 1.27 1.27 1.29 1.33 1.29 propane CH3t,7.30.900.900.900.890.860.840.880.870.900.900.910.88 CH2sept,7.3 1.33 1.32 1.32 1.32 1.26 1.26 1.31 1.29 1.33 1.33 1.34 1.30 2-propanol CH3d,6 1.08 1.17 1.220.950.95 1.04 1.10 1.04 1.09 1.20 1.50 1.17 CH sept,6 3.82 3.97 4.04 3.65 3.67 3.82 3.90 3.78 3.87 4.05 3.92 4.02 propylene CH3dt,6.4,1.5 1.69 1.71 1.73 1.55 1.55 1.58 1.68 1.68 1.70 1.70 1.70 1.70 CH2(1)dm,10 4.89 4.93 4.94 4.92 4.95 4.91 4.90 4.94 4.93 4.93 4.91 4.95CH2(2)dm,17 4.99 5.03 5.03 4.98 5.01 4.98 5.00 5.03 5.04 5.03 5.01 5.06CH m 5.79 5.84 5.83 5.70 5.72 5.72 5.81 5.80 5.85 5.87 5.82 5.90 pyridine CH(2,6)m8.548.598.628.478.538.518.588.588.578.458.538.52 CH(3,5)m7.257.287.29 6.67 6.66 6.907.357.397.337.407.447.45CH(4)m7.657.687.68 6.99 6.987.257.767.797.737.827.857.87 pyrrole NH br t9.968.698.407.717.808.6110.0210.759.27CH(2,5)m 6.66 6.79 6.83 6.43 6.48 6.62 6.77 6.73 6.75 6.84 6.72 6.93CH(3,4)m 6.02 6.19 6.26 6.27 6.37 6.27 6.07 6.01 6.10 6.24 6.08 6.26 pyrrolidine h CH2(2,5)m 2.75 2.82 2.87 2.54 2.54 2.64 2.67 2.75 3.11 2.80 3.07 CH2(3,4)m 1.59 1.67 1.68 1.36 1.33 1.43 1.55 1.61 1.93 1.72 1.87 silicone grease CH3s0.110.090.070.260.290.140.13-0.060.080.160.10 tetrahydrofuran CH2(2,5)m 3.62 3.69 3.76 3.54 3.57 3.59 3.63 3.60 3.64 3.78 3.71 3.74 CH2(3,4)m 1.79 1.82 1.85 1.43 1.40 1.55 1.79 1.76 1.80 1.91 1.87 1.88 toluene CH3s 2.31 2.34 2.36 2.11 2.11 2.16 2.32 2.30 2.33 2.33 2.32 CH(2,4,6)m7.107.157.17 6.96-7.017.027.01-7.087.10-7.207.187.10-7.307.10-7.307.16CH(3,5)m7.197.247.257.097.137.10-7.177.10-7.207.257.10-7.307.10-7.307.16 triethylamine CH3t,70.970.99 1.030.950.960.930.960.930.96 1.31 1.050.99 CH2q,7 2.46 2.48 2.53 2.39 2.40 2.39 2.45 2.43 2.45 3.12 2.58 2.57a Except for the compounds in solutions8-10,as well as the gas samples,hexamethylbenzene,and the corrected values mentioned in the Supporting Information,all data for the solvents CDCl3,C6D6,(CD3)2CO,(CD3)2SO,CD3CN,CD3OD,and D2O were previously reported in ref2.b A signal for HDO is also observed in(CD3)2SO(3.30ppm)and(CD3)2CO(2.81ppm),often seen as a1:1:1triplet(2J H,D=1Hz).c Not all OH signals were observable.d In some solvents,the coupling interaction between the CH2and the OH protons may be observed(J=5Hz).e In CD3CN,the OH proton was seen as a multiplet at2.69ppm,as well as extra coupling to the CH2resonance.f Apiezon brand H grease.g In some solvents,a coupling interaction between the CH3and the OH protons may be observed(J=5.5Hz).h Pyrrolidine was observed to react with(CD3)2CO.Article Organometallics,Vol.XXX,No.XX,XXXX CTable2.13C{1H}NMR Data acarbon THF-d8CD2Cl2CDCl3toluene-d8C6D6C6D5Cl(CD3)2CO(CD3)2SO CD3CN TFE-d3CD3OD D2O solvent signals67.2153.8477.16137.48128.06134.1929.8439.52 1.3261.5049.0025.31128.87129.26206.26118.26126.28127.96128.25125.13125.9620.43acetic acid CO171.69175.85175.99175.30175.82175.67172.31171.93173.21177.96175.11177.21 CH320.1320.9120.8120.2720.3720.4020.5120.9520.7320.9120.5621.03acetone CO204.19206.78207.07204.00204.43204.83205.87206.31207.4332.35209.67215.94 CH330.1731.0030.9230.0330.1430.1230.6030.5630.91214.9830.6730.89acetonitrile CN116.79116.92116.43115.76116.02115.93117.60117.91118.26118.95118.06119.68 CH30.45 2.03 1.890.030.200.63 1.12 1.03 1.79 1.000.85 1.47 benzene CH128.84128.68128.37128.57128.62128.38129.15128.30129.32129.84129.34tert-butyl alcohol(CH3)3C67.5069.1169.1568.1268.1968.1968.1366.8868.7472.3569.4070.36(C H3)3C30.5731.4631.2530.4930.4731.1330.7230.3830.6831.0730.9130.29carbon dioxide CO2125.69125.26124.99124.86124.76126.08125.81124.21125.89126.92126.31carbon disulfide CS2193.37192.95192.83192.71192.69192.49193.58192.63193.60196.26193.82197.25carbon tetrachloride CCl496.8996.5296.3496.5796.4496.3896.6595.4496.6897.7497.2196.73 chloroform CH79.2477.9977.3677.8977.7977.6779.1979.1679.1778.8379.4418-crown-6CH271.3470.4770.5570.8670.5970.5571.2569.8571.2270.8071.4770.14cyclohexane CH227.5827.3826.9427.3127.2326.9927.5126.3327.6328.3427.961,2-dichloroethane CH244.6444.3543.5043.4043.5943.6045.2545.0245.5445.2845.11dichloromethane CH254.6754.2453.5253.4753.4653.5454.9554.8455.3254.4654.78diethyl ether CH315.4915.4415.2015.4715.4615.3515.7815.1215.6315.3315.4614.77CH266.1466.1165.9165.9465.9465.7966.1262.0566.3267.5566.8866.42 diglyme CH358.7258.9559.0158.6258.6658.4258.7757.9858.9059.4059.0658.67CH271.1770.7070.5170.9270.8770.5671.0369.5470.9973.0571.3370.05CH272.7272.2571.9072.3972.3572.0772.6371.2572.6371.3372.9271.63 dimethylformamide CH161.96162.57162.62161.93162.13162.01162.79162.29163.31166.01164.73165.53CH335.6536.5636.5035.2235.2535.4536.1535.7336.5737.7636.8937.54CH330.7031.3931.4530.6430.7230.7131.0330.7331.3230.9631.6132.031,4-dioxane CH267.6567.4767.1467.1767.1666.9567.6066.3667.7268.5268.1167.19 DME CH358.7259.0259.0858.6358.6858.3158.4558.0358.8959.5259.0658.67CH272.5872.2471.8472.2572.2171.8172.4771.1772.4772.8772.7271.49 ethane CH3 6.79 6.91 6.89 6.94 6.96 6.91 6.88 6.61 6.997.01 6.98ethanol CH318.9018.6918.4118.7818.7218.5518.8918.5118.8018.1118.4017.47CH257.6058.5758.2857.8157.8657.6357.7256.0757.9659.6858.2658.05 ethyl acetate C H3CO20.4521.1521.0420.4620.5620.5020.8320.6821.1621.1820.8821.15CO170.32171.24171.36170.02170.44170.20170.96170.31171.68175.55172.89175.26CH260.3060.6360.4960.0860.2160.0660.5659.7460.9862.7061.5062.32CH314.3714.3714.1914.2314.1914.0714.5014.4014.5414.3614.4913.92 ethylene CH2123.09123.20123.13122.92122.96122.95123.47123.52123.69124.08123.46 ethylene glycol CH264.3564.0863.7964.2964.3464.0364.2662.7664.2264.8764.3063.17H grease b CH230.4530.1429.7130.3130.2230.11hexamethylbenzene C131.88132.09132.21131.72131.79131.54132.22131.10132.61134.04132.53CH316.7116.9316.9816.8416.9516.6816.8616.6016.9417.0416.90n-hexane CH314.2214.2814.1414.3414.3214.1814.3413.8814.4314.6314.45CH2(2,5)23.3323.0722.7023.1223.0422.8623.2822.0523.4024.0623.68CH2(3,4)32.3432.0131.6432.0631.9631.7732.3030.9532.3633.1732.73HMDSO CH3 1.83 1.96 1.97 1.99 2.05 1.92 2.01 1.96 2.07 2.09 1.99 2.31 HMPA c CH336.8936.9936.8736.8036.8836.6437.0436.4237.1037.2137.0036.46 imidazole CH(2)135.72135.76135.38135.57135.76135.50135.89135.15136.33136.58136.31136.65CH(4,5)122.20122.16122.00122.13122.16121.96122.31121.55122.78122.93122.60122.43 methane CH4-4.90-4.33-4.63-4.34-4.29-4.33-5.33-4.01-4.61-5.88-4.90 methanol CH349.6450.4550.4149.9049.9749.6649.7748.5949.9050.6749.8649.50d nitromethane CH362.4963.0362.5061.1461.1661.6863.2163.2863.6663.1763.0863.22n-pentane CH314.1814.2414.0814.2714.2514.1014.2913.2814.3714.5414.39 CH2(2,4)23.0022.7722.3822.7922.7222.5422.9821.7023.0823.7523.38CH2(3)34.8734.5734.1634.5434.4534.2634.8333.4834.8935.7635.30propane CH316.6016.6316.6316.6516.6616.5616.6816.3416.7316.9316.80 CH216.8216.6316.3716.6316.6016.4816.7815.6716.9117.4617.192-propanol CH325.7025.4325.1425.2425.1825.1425.6725.4325.5525.2125.2724.38 CH66.1464.6764.5064.1264.2364.1863.8564.9264.3066.6964.7164.88 propylene CH319.2719.4719.5019.3219.3819.3219.4219.2019.4819.6319.50 CH2115.74115.70115.74115.89115.92115.86116.03116.07116.12116.38116.04CH134.02134.21133.91133.61133.69133.57134.34133.55134.78136.00134.61pyridine CH(2,6)150.57150.27149.90150.25150.27149.93150.67149.58150.76149.76150.07149.18 CH(3,5)124.08124.06123.75123.46123.58123.49124.57123.84127.76126.27125.53125.12CH(4)135.99136.16135.96135.17135.28135.32136.56136.05136.89139.62138.35138.27 pyrrole CH(2,5)118.03117.93117.77117.61117.78117.65117.98117.32118.47119.61118.28119.06 CH(3,4)107.74108.02107.98108.15108.21108.03108.04107.07108.31108.85108.11107.83 pyrrolidine e CH2(2,5)45.8247.0246.9347.1246.8646.7546.5147.5747.4347.2346.83 CH2(3,4)26.1725.8325.5625.7525.6525.5925.2626.3425.7326.2925.86 silicone grease CH3 1.20 1.22 1.19 1.37 1.38 1.09 1.40 2.87 2.10 tetrahydrofuran CH2(2,5)68.0368.1667.9767.7567.8067.6468.0767.0368.3369.5368.8368.68 CH2(3,4)26.1925.9825.6225.7925.7225.6826.1525.1426.2726.6926.4825.67 toluene CH321.2921.5321.4621.3721.1021.2321.4620.9921.5021.6221.50 C(1)138.24138.36137.89137.84137.91137.65138.48137.35138.90139.92138.85CH(2,6)129.47129.35129.07129.33129.33129.12129.76128.88129.94130.58129.91CH(3,5)128.71128.54128.26128.51128.56128.31129.03128.18129.23129.79129.20CH(4)125.84125.62125.33125.66125.68125.43126.12125.29126.28126.82126.29 triethylamine CH312.5112.1211.6112.3912.3511.8712.4911.7412.389.5111.099.07 CH247.1846.7546.2546.8246.7746.3647.0745.7447.1048.4546.9647.19a Except for the compounds in solutions8-10,as well as the gas samples,hexamethylbenzene,and the corrected values mentioned in the Supporting Information,all data for the solvents CDCl3,C6D6,(CD3)2CO,(CD3)2SO,CD3CN,CD3OD,and D2O were previously reported in ref2.b Apiezon c2d eD Organometallics,Vol.XXX,No.XX,XXXX Fulmer et al.1,2-dimethoxyethane(DME),nitromethane,poly(dimethylsiloxane) (silicone grease),triethylamine;(solution7)diglyme,dimethyl-acetamide,ethylene glycol,ethyl methyl ketone;(solution8) allyl acetate,2,6-di-tert-butyl-4-methoxyphenol(BHA),long-chain,linear aliphatic hydrocarbons from pump oil;4(solu-tion9)benzaldehyde,carbon disulfide,carbon tetrachloride, cyclohexanone,dimethyl malonate,furan,Apiezon H grease (H grease);(solution10)18-crown-6,diallyl carbonate,dimethyl carbonate,hexamethyldisiloxane(HMDSO),imidazole,pyrrole, pyrrolidine.5In the case of TFE-d3,nitromethane was omitted from solution6and run separately,since the protons of nitro-methane exchange with deuterium from TFE-d3in the presence of triethylamine.In the case of(CD3)2CO,pyrrolidine was omitted from solution10,since the two compounds were observed to react with each other.The gases used in this study included hydrogen,methane,ethane,propane,ethylene,propylene,and carbon dioxide.Before examining the various standard contaminant solu-tions by1H NMR spectroscopy,solvent residual signals6and chemical shifts for H2O7for each NMR solvent were refer-enced against tetramethylsilane(TMS,δ0ppm)and reported. Before collecting13C{1H}NMR spectral data,solvent signals6 were recorded with reference to the signal of a TMS internal standard.For D2O,1H NMR spectra were referenced to the methyl signal(δ0ppm)of sodium3-(trimethylsilyl)propane-sulfonate,8,9and13C{1H}NMR spectra were referenced to the signal for the methyl group of methanol(one drop,added as an internal standard),which was set to49.50ppm.2In a typical experiment for collecting1H NMR spectral data,a 3μL sample of a standard contaminant solution was added to an NMR tube containing approximately0.4mL of a deuterated solvent.For13C{1H}NMR spectral data collection,an approxi-mately50μL sample of the standard contaminant solution was added.When there was any uncertainty in the assignment of a resonance,the solution was spiked with an additional1-2μL of the impurity in question to accurately identify its chemical shift.In cases where the chemical shifts of resonances were highly dependent on the concentration of the impurities pre-sent,ambiguous resonances were instead resolved via gradient-selected heteronuclear single-quantum coherence(gs-HSQC) and gradient-selected heteronuclear multiple-quantum coherence (gs-HMQC)NMR spectroscopies.For the experiments involving gases,a J.Young NMR tube containing approximately0.4mL of NMR solvent was first degassed with three freeze-pump-thaw ing a vacuum line equipped with a gas manifold,1atm of the desired gas was added to the tube.Each gas was run separately,degassing between each gas sample.Results and DiscussionChemical shifts for each of the impurities are reported in the tables:1H and13C{1H}NMR spectral data of all sub-strates are presented in Tables1and2,respectively.Notably, physically larger tables,containing all the data from Tables1 and2as well as the chemical shifts of additional organic compounds,are provided in the Supporting Information. Unless noted otherwise,coupling constants(reported in Hz) and resonance multiplicities(abbreviated as follows:s= singlet,d=doublet,t=triplet,q=quartet,p=pentet, sept=septet,m=multiplet,br=broad)were observed to be solvent-independent.It was noted that the amount of gas dissolved in solution gave1H NMR signal integrations that were qualitatively comparable to those for the solutions made with the3μL additions of the liquid or solid contaminants.However,typi-cally in order to observe signals for the gas samples by13C{1H} NMR spectroscopy,additional time for data collection was required.The solubility of each gas in D2O was extremely limited,making13C detection impractical.Of all the gases, methane required the most number of transients in order to obtain an observable signal by13C{1H}NMR spectroscopy. In most cases,the13C chemical shift of methane was acquired through the use of gs-HMQC NMR spectroscopy to provide enhanced sensitivity.In order to reflect what would be ob-served in typical NMR-scale experiments,13C detection was not pursued with isotopically enriched gases.A number of misreported values were discovered in the years since the original publication10and in the preparation of this paper. These are detailed in the Supporting Information,and the values are now correctly listed in Tables1and2. Acknowledgment.G.R.F.and K.I.G.thank the Depart-ment of Energy(Contract No.DE-FG02-06ER15765)for support.A.J.M.M.and J.E.B.thank the Moore Founda-tion for support.N.H.S.and B.M.S.thank Abbott Labora-tories,Amgen,Merck,Bristol-Myers Squibb,Boehringer Ingelheim,the Gordon and Betty Moore Foundation,and Caltech for financial support.Supporting Information Available:Large-format tables of the all the NMR data.This material is available free of charge via the Internet at .(4)VWR brand vacuum pump oil#19.(5)The components of solution10were stable together in dilute solution but unstable when neat mixtures were prepared.In general,it was observed that the nitrogen-containing compounds and possibly 18-crown-6catalyzed the hydrolysis of the carbonates,reacted directly with them,or both.Therefore,for the purpose of storage,the solution was partitioned into two subsolutions:(solution10A)18-crown-6, imidazole,pyrrole,pyrrolidine;(solution10B)diallyl carbonate,di-methyl carbonate,hexamethyldisiloxane.These subsolutions were stable for long periods as neat mixtures and were combined to form solution10by adding equal portions to an NMR tube containing the desired deuterated solvent.(6)For1H NMR spectra,the solvent residual signals arise from the proton of isotopomers containing one less deuterium atom than the perdeuterated solvent:e.g.,CDHCl2in CD2Cl2.For13C NMR spectra, the solvent signals arise from the13C atoms at natural abundance in the perdeuterated solvent.(7)The chemical shift for H2O can vary depending on the tempera-ture,[H2O],and the solutes present:e.g.,a downfield shift may be observed in the presence of any hydrogen bond acceptors.For more information see page75of ref1.(8)Harris,R.K.;Becker,E.D.;Cabral de Menezes,S.M.;Granger, P.;Hoffman,R.E.;Zilm,K.W.Pure Appl.Chem.2008,80,59.(9)For information on the temperature dependence of HDO chemi-cal shifts in D2O,see ref2.(10)The misreported value for acetonitrile in C6D6from the original paper2was also pointed out by Dr.Jongwook Choi,to whom we are grateful.Supporting InformationNMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to theOrganometallic ChemistGregory R. Fulmer,*,1 Alexander J. M. Miller,2 Nathaniel H. Sherden,2 Hugo E. Gottlieb,3 Abraham Nudelman,3 Brian M. Stoltz,2 John E. Bercaw,2 and Karen I.Goldberg11 Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700;2 Arnold and Mabel Beckman Laboratories of Chemical Synthesis, and Caltech Center for Catalysis and Chemical Synthesis, Division of Chemistry and Chemical Engineering California Institute of Technology,Pasadena, California 91125;3 Department of Chemistry, Bar Ilan University, Ramat Gan 52900, Israel.Corrections and Comments........................................................................................................S2 1H NMR Data (Table S1)............................................................................................................S3 13C NMR Data (Table S2)...........................................................................................................S5 Individual Solvent Tables – NMR Data Sorted by Chemical Shift (Tables S3–S26)............S7 References..................................................................................................................................S19Corrections and CommentsIn the preparation of this manuscript, several errors were discovered in the original paper1and are reported herein. While comparing the 1H NMR spectral data obtained in toluene-d8 to that in C6D6, it was discovered that the 1H NMR chemical shifts for acetic acid (C H3), acetonitrile (C H3) and tert-butyl alcohol (O H) in C6D6had each been misreported at 1.55 ppm in the original paper; the values have now been correctly listed as 1.52, 0.58, and 0.63 ppm, respectively. The original paper's assignments for BHT's C(3,5) and C(4) in C6D6, (CD3)2CO, (CD3)2SO, CD3CN, and CD3OD were reversed and are now corrected. The resonances for 1,2-dimethoxyethane (C H2) in (CD3)2CO, silicone grease (C H3) in CDCl3, and 2-propanol (C H3) in CD3OD have been corrected and are reported as 72.47, 1.04, and 1.15 ppm, respectively. No other significant differences were discovered when comparing our data to that which had been previously reported; however, we have additionally provided the O H resonance for ethanol in C6D6 (0.50 ppm), the C H3 resonance for silicone grease in (CD3)2SO (–0.06 ppm), and replaced the “grease” entry (formerly motor oil1) with VWR vacuum pump oil #19, which is now reported in each deuterated solvent.Table S1.1H NMR Data2proton mult THF-d8CD2Cl2CDCl3toluene-d8C6D6C6D5Cl(CD3)2CO(CD3)2SO CD3CN TFE-d3CD3OD D2O solvent residual signals 1.72 5.327.26 2.087.16 6.96 2.05 2.50 1.94 5.02 3.31 4.793.58 6.97 6.99 3.887.017.147.09water OH s 2.46 1.52 1.560.430.40 1.03 2.843 3.333 2.13 3.66 4.87-acetic acid CH3s 1.89 2.06 2.10 1.57 1.52 1.76 1.96 1.91 1.96 2.06 1.99 2.08 acetone CH3s 2.05 2.12 2.17 1.57 1.55 1.77 2.09 2.09 2.08 2.19 2.15 2.22 acetonitrile CH3s 1.95 1.97 2.100.690.58 1.21 2.05 2.07 1.96 1.95 2.03 2.06 allyl acetate C H CH2ddt 5.90 5.92 5.93 5.674 5.684 5.77 5.92 5.91 5.93 5.93 5.94 5.99 CHC H2(1)ddt 5.27 5.31 5.32 5.05 5.06 5.15 5.29 5.29 5.29 5.32 5.30 5.37CHC H2(2)ddt 5.15 5.22 5.24 4.94 4.94 5.04 5.18 5.20 5.21 5.25 5.21 5.30 CH2ddd 4.50 4.55 4.57 4.34 4.38 4.44 4.53 4.52 4.53 4.58 4.56 4.62CH3s 1.98 2.05 2.09 1.63 1.63 1.80 2.02 2.03 2.02 2.07 2.05 2.13 benzaldehyde HCO s9.9810.0110.039.579.649.7710.0510.0210.019.8810.009.96 CH(2,6)m7.86–7.887.87–7.897.88–7.917.45–7.477.49–7.537.59–7.617.92–7.947.91–7.937.89–7.917.90–7.927.90–7.937.97–7.99CH(3,5)m7.51–7.557.53–7.577.51–7.57 6.95–6.99 6.93–6.997.15–7.197.59–7.637.61–7.677.57–7.617.56–7.597.56–7.607.57–7.66CH(4)m7.60–7.647.63–7.677.61–7.657.03–7.077.01–7.077.24–7.287.69–7.737.69–7.757.67–7.717.68–7.727.66–7.707.76–7.80 benzene CH s7.317.357.367.127.157.207.367.377.377.367.33-tert-butyl alcohol CH3s 1.15 1.24 1.28 1.03 1.05 1.12 1.18 1.11 1.16 1.28 1.40 1.24 OH s5 3.16--0.580.63 1.30- 4.19 2.18 2.20--BHA ArH s 6.68 6.73 6.76 6.83 6.93 6.83 6.72 6.62 6.73 6.87 6.71-OH s5 5.64 4.76 4.76 4.45 4.53 4.62 5.65 6.52 4.98- 4.85-ArOCH3s 3.68 3.73 3.77 3.48 3.48 3.61 3.72 3.66 3.72 3.79 3.72-ArC(CH3)3s 1.40 1.42 1.44 1.34 1.41 1.37 1.41 1.36 1.40 1.44 1.41-BHT ArH s 6.92 6.97 6.98 6.997.05 6.97 6.96 6.87 6.977.06 6.92-OH s5 5.81 5.00 5.01 4.72 4.79 5.50- 6.65 5.20---ArCH3s 2.21 2.25 2.27 2.23 2.24 2.20 2.22 2.18 2.22 2.24 2.21-ArC(CH3)3s 1.40 1.42 1.43 1.36 1.38 1.37 1.41 1.36 1.39 1.43 1.40-chloroform CH s7.897.327.26 6.10 6.15 6.748.028.327.587.337.90-18-crown-6CH2s 3.57 3.59 3.67 3.36 3.39 3.41 3.59 3.51 3.51 3.64 3.64 3.80 cyclohexane CH2s 1.44 1.44 1.43 1.40 1.40 1.37 1.43 1.40 1.44 1.47 1.45-cyclohexanone CH2(2,6)t 2.24 2.29 2.33 1.95 1.98 2.08 2.27 2.25 2.27 2.38 2.34 2.40 CH2(3,5)m 1.77–1.82 1.81–1.87 1.84–1.86 1.33–1.39 1.28–1.37 1.48–1.53 1.79–1.83 1.74–1.78 1.79–1.84 1.87–1.92 1.85–1.87 1.85–1.90CH2(4)m 1.68–1.71 1.69–1.72 1.71–1.73 1.16–1.20 1.08–1.16 1.33–1.37 1.70–1.74 1.64–1.66 1.67–1.72 1.75–1.78 1.74–1.76 1.70–1.75 diallyl carbonate C H CH2ddt 5.92 5.95 5.94 5.63 5.65 5.75 5.96 5.93 5.96 5.92 5.94 5.99 CHC H2(1)ddt 5.31 5.35 5.37 5.09 5.09 5.17 5.35 5.33 5.34 5.35 5.34 5.40CHC H2(2)ddt 5.19 5.26 5.27 4.92 4.92 5.03 5.23 5.25 5.25 5.28 5.25 5.32 CH2ddd 4.58 4.61 4.64 4.34 4.38 4.46 4.62 4.61 4.61 4.62 4.61 4.69 1,2-dichloroethane CH2s 3.77 3.76 3.73 2.91 2.90 3.26 3.87 3.90 3.81 3.71 3.78-dichloromethane CH2s 5.51 5.33 5.30 4.32 4.27 4.77 5.63 5.76 5.44 5.24 5.49-diethyl ether CH3t, 7 1.12 1.15 1.21 1.10 1.11 1.10 1.11 1.09 1.12 1.20 1.18 1.17 CH2q, 7 3.38 3.43 3.48 3.25 3.26 3.31 3.41 3.38 3.42 3.58 3.49 3.56 diglyme CH2m 3.43 3.57 3.65 3.43 3.46 3.49 3.56 3.51 3.53 3.67 3.61 3.67 CH2m 3.53 3.50 3.57 3.31 3.34 3.37 3.47 3.38 3.45 3.62 3.58 3.61OCH3s 3.28 3.33 3.39 3.12 3.11 3.16 3.28 3.24 3.29 3.41 3.35 3.37 1,2-dimethoxyethane CH3s 3.28 3.34 3.40 3.12 3.12 3.17 3.28 3.24 3.28 3.40 3.35 3.37 CH2s 3.43 3.49 3.55 3.31 3.33 3.37 3.46 3.43 3.45 3.61 3.52 3.60 dimethylacetamide CH3CO s 1.94 2.02 2.09 1.59 1.60 1.74 1.97 1.96 1.97 2.09 2.07 2.08 NCH3s 2.95 2.97 3.02 2.56 2.57 2.65 3.00 2.94 2.96 3.05 3.31 3.06NCH3s 2.82 2.87 2.94 2.11 2.05 2.42 2.83 2.78 2.83 2.94 2.92 2.90 dimethyl carbonate CH3s 3.69 3.75 3.79 3.31 3.30 3.48 3.72 3.69 3.72 3.77 3.74 3.69 dimethyl malonate CH3s 3.65 3.72 3.75 3.24 3.23 3.41 3.68 3.65 3.68 3.76 3.72 3.78 CH2s 3.35 3.37 3.40 2.92 2.97 3.15 3.42 3.53 3.38 3.41 3.44 3.60 dimethylformamide CH s7.917.968.027.577.637.737.967.957.927.867.977.92 CH3s 2.88 2.91 2.96 2.37 2.36 2.51 2.94 2.89 2.89 2.98 2.99 3.01CH3s 2.76 2.82 2.88 1.96 1.86 2.30 2.78 2.73 2.77 2.88 2.86 2.85 dimethyl sulfoxide CH3s 2.45 2.55 2.62 1.64 1.68 2.03 2.52 2.54 2.50 2.63 2.65 2.71 1,4-dioxane CH2s 3.56 3.65 3.71 3.33 3.35 3.45 3.59 3.57 3.60 3.76 3.66 3.75 ethane CH3s0.850.850.870.810.800.790.830.820.850.850.850.82 ethanol CH3t, 7 1.10 1.19 1.250.970.96 1.06 1.12 1.06 1.12 1.22 1.19 1.17 CH2q, 76 3.51 3.66 3.72 3.36 3.34 3.51 3.57 3.44 3.54 3.71 3.60 3.65OH s5,6 3.30 1.33 1.320.830.50 1.39 3.39 4.63 2.47---ethyl acetate CH3CO s 1.94 2.00 2.05 1.69 1.65 1.78 1.97 1.99 1.97 2.03 2.01 2.07C H2CH3q, 7 4.04 4.08 4.12 3.87 3.89 3.96 4.05 4.03 4.06 4.14 4.09 4.14CH2C H3t, 7 1.19 1.23 1.260.940.92 1.04 1.20 1.17 1.20 1.26 1.24 1.24 ethyl methyl ketone CH3CO s 2.03 2.09 2.14 1.59 1.58 1.78 2.07 2.07 2.06 2.16 2.12 2.19C H2CH3q, 7 2.39 2.43 2.46 1.82 1.81 2.06 2.45 2.43 2.43 2.49 2.50 3.18CH2C H3t, 70.96 1.00 1.060.840.850.890.960.910.96 1.05 1.01 1.26 ethylene CH2s 5.36 5.40 5.40 5.25 5.25 5.29 5.38 5.41 5.41 5.40 5.39 5.44 ethylene glycol CH2s7 3.48 3.66 3.76 3.36 3.41 3.58 3.28 3.34 3.51 3.72 3.59 3.65 furan CH(2,5)dd7.487.467.457.107.137.247.567.677.527.447.497.57 CH(3,4)dd 6.37 6.41 6.40 6.07 6.08 6.19 6.43 6.47 6.44 6.42 6.40 6.51H grease8CH3m0.85–0.910.84–0.900.84–0.870.89–0.960.90–0.980.86–0.920.900.82–0.88-0.88–0.940.86–0.93-CH2br s 1.29 1.27 1.25 1.33 1.32 1.30 1.29 1.24- 1.33 1.29-hexamethylbenzene CH3s 2.18 2.20 2.24 2.10 2.13 2.10 2.17 2.14 2.19 2.24 2.19-hexamethyldisiloxane CH3s0.070.070.070.100.120.100.070.060.070.080.070.28。

核磁谱图nmr常见溶剂峰杂质峰分析_中文版

核磁谱图nmr常见溶剂峰杂质峰分析_中文版

测试核磁的样品一般要求比较纯，并且能够溶解在氘代试剂中，这样才能测得高分辨率的图谱。

为不干扰谱图，所用溶剂分子中的氢都应被氘取代，但难免有氢的残余（1%左右），这样就会产生溶剂峰；除了残存的质子峰外，溶剂中有时会有微量的H2O而产生水峰，而且这个H2O峰的位置也会因溶剂的不同而不同；另外，在样品（或制备过程）中，也难免会残留一些杂质，在图谱上就会有杂质峰，应注意识别。

常用氘代溶剂和杂质峰在1H谱中的化学位移? ?单位：ppm溶剂? ? —?? CDCl3?? (CD3)2CO? (CD3)2SO? C6D6?? ?CD3CN?? CD3OH?? D2O溶剂峰—7.26 2.05 2.49 7.16 1.94 3.31 4.80水峰— 1.56 2.84 3.33 0.40 2.13 4.87 —乙酸— 2.10 1.96 1.91 1.55 1.96 1.99 2.08丙酮— 2.17 2.09 2.09 1.55 2.08 2.15 2.22乙腈— 2.10 2.05 2.07 1.55 1.96 2.03 2.06苯—7.36 7.36 7.37 7.15 7.37 7.33 —叔丁醇CH3 1.28 1.18 1.11 1.05 1.16 1.40 1.24OH —— 4.19 1.55 2.18 ——叔丁基甲醚CCH3 1.19 1.13 1.11 1.07 1.14 1.15 1.21OCH3 3.22 3.13 3.08 3.04 3.13 3.20 3.22 氯仿—7.26 8.02 8.32 6.15 7.58 7.90 —环己烷— 1.43 1.43 1.40 1.40 1.44 1.45 —1,2-二氯甲烷 3.73 3.87 3.90 2.90 3.81 3.78 —二氯甲烷— 5.30 5.63 5.76 4.27 5.44 5.49 —乙醚 CH3(t) 1.21 1.11 1.09 1.11 1.12 1.18 1.17CH2(q) 3.48 3.41 3.38 3.26 3.42 3.49 3.56 二甲基甲酰胺CH 8.02 7.96 7.95 7.63 7.92 7.79 7.92CH3 2.96 2.94 2.89 2.36 2.89 2.99 3.01CH3 2.88 2.78 2.73 1.86 2.77 2.86 2.85 二甲基亚砜— 2.62 2.52 2.54 1.68 2.50 2.65 2.71二氧杂环— 3.71 3.59 3.57 3.35 3.60 3.66 3.75 乙醇 CH3(t) 1.25 1.12 1.06 0.96 1.12 1.19 1.17 CH2(q) 3.72 3.57 3.44 3.34 3.54 3.60 3.65OH(s) 1.32 3.39 3.63 — 2.47 ——乙酸乙酯CH3CO 2.05 1.97 1.99 1.65 1.97 2.01 2.07 OCH2(q) 4.12 4.05 4.03 3.89 4.06 4.09 4.14CH3(t) 1.26 1.20 1.17 0.92 1.20 1.24 1.24甲乙酮CH3CO 2.14 2.07 2.07 1.58 2.06 2.12 2.19 CH2(q) 2.46 2.45 2.43 1.81 2.43 2.50 3.18CH3(t) 1.06 0.96 0.91 0.85 0.96 1.01 1.26乙二醇— 3.76 3.28 3.34 3.41 3.51 3.59 3.65润滑脂 CH3(m) 0.86 0.87 —0.92 0.86 0.88 —CH2(br) 1.26 1.29 — 1.36 1.27 1.29 —正己烷CH3(t) 0.88 0.88 0.86 0.89 0.89 0.90 —CH2 (m) 1.26 1.28 1.25 1.24 1.28 1.29 —甲醇CH3 3.49 3.31 3.16 3.07 3.28 3.34 3.34 OH 1.09 3.12 4.01 2.16 ——正戊烷 CH3(t) 0.88 0.88 0.86 0.87 0.89 0.90 —CH2(m) 1.27 1.27 1.27 1.23 1.29 1.29 —异丙醇CH3(d) 1.22 1.10 1.04 0.95 1.09 1.50 1.17 CH 4.04 3.90 3.78 3.67 3.87 3.92 4.02 硅脂—0.07 0.13 —0.29 0.08 0.10 —四氢呋喃 CH2 1.85 1.79 1.76 1.40 1.80 1.87 1.88 CH2O 3.76 3.63 3.60 3.57 3.64 3.71 3.74 甲苯 CH3 2.36 2.32 2.30 2.11 2.33 2.32 —CH（o/p）7.17 7.20 7.18 7.02 7.30 7.16 —CH（m） 7.25 7.20 7.25 7.13 7.30 7.16 —三乙基胺 CH3 1.03 0.96 0.93 0.96 0.96 1.05 0.99 CH2 2.53 2.45 2.43 2.40 2.45 2.58 2.57 石油醚—0.5-1.5 0.6-1.9 —————。

常见氘代溶剂和杂质在氢谱中的峰

常见氘代溶剂和杂质在氢谱中的峰

测试核磁的样品一般要求比较纯，并且能够溶解在氘代试剂中，这样才能测得高分辨率的图谱。

为不干扰谱图，所用溶剂分子中的氢都应被氘取代，但难免有氢的残余（1%左右），这样就会产生溶剂峰；除了残存的质子峰外，溶剂中有时会有微量的H2O而产生水峰，而且这个H2O峰的位置也会因溶剂的不同而不同；另外，在样品（或制备过程）中，也难免会残留一些杂质，在图谱上就会有杂质峰，应注意识别。

以下给出了一些常见溶剂峰和杂质峰的化学位移：常用氘代溶剂和杂质峰在1H谱中的化学位移单位：ppm溶剂 CDCl3 (CD3)2CO (CD3)2SO C6D6 CD3CN CD3OH D2O溶剂峰水峰—乙酸丙酮乙腈苯—叔丁醇 CH3OH ————叔丁基甲醚CCH3OCH3氯仿—环己烷—1,2-二氯甲烷—二氯甲烷—乙醚CH3(t)CH2(q)二甲基甲酰胺CHCH3CH3二甲基亚砜二氧杂环乙醇CH3(t)OH(s) ———乙酸乙酯CH3COOCH2(q)CH3(t)甲乙酮CH3COCH2(q)CH3(t)乙二醇润滑脂CH3(m) ——CH2(br) ——正己烷CH3(t) —CH2 (m) —甲醇CH3OH ——正戊烷CH3(t) —CH2(m) —异丙醇CH3(d)CH硅脂——四氢呋喃CH2CH2O甲苯CH3 —CH（o/p）—三乙基胺CH3CH2石油醚—————。

精选-常见氘代溶剂和杂质在氢谱中的峰

精选-常见氘代溶剂和杂质在氢谱中的峰

常用氘代溶剂和杂质峰在1H谱中的化学位移测试核磁的样品一般要求比较纯，并且能够溶解在氘代试剂中，这样才能测得高分辨率的图谱。

为不干扰谱图，所用溶剂分子中的氢都应被氘取代，但难免有氢的残余( 1%左右)，这样就会产生溶剂峰;除了残存的质子峰外，溶剂中有时会有微量的H20而产生水峰，而且这个H20峰的位置也会因溶剂的不同而不同；另外，在样品(或制备过程)中，也难免会残留一些杂质，在图谱上就会有杂质峰，应注意识别。

以下给出了一些常见溶剂峰和杂质峰的化学位移：常用氘代溶剂和杂质峰在1H谱中的化学位移单位：ppm溶齐U CDCI3 (CD3)2CO (CD3)2SO C6D6 CD3CN CD30H D20溶剂峰7.26 2.05 2.49 7.16 1.943.314.80水峰 1.56 2.84 3.33 0.40 2.13 4.87乙酸 2.10 1.96 1.91 1.55 1.96 1.99 2.08丙酮 2.17 2.09 2.09 1.55 2.08 2.15 2.22乙腈 2.10 2.05 2.07 1.55 1.96 2.03 2.06苯7.36 7.36 7.37 7.15 7.37 7.33叔丁醇CH3 1.28 1.18 1.11 1.05 1.16 1.40 1.24OH———— 4.19 1.55 2.18叔丁基甲醚CCH3 1.19 1.13 1.11 1.07 1.141.151.21OCH3 3.22 3.13 3.08 3.04 3.13 3.20 3.22 氯仿7.26 8.02 8.32 6.15 7.58 7.90环己烷 1.43 1.43 1.40 1.40 1.44 1.451,2-二氯甲烷 3.73 3.87 3.90 2.90 3.81 3.78二氯甲烷 5.30 5.63 5.76 4.27 5.44 5.49乙醚CH3(t) 1.21 1.11 1.09 1.11 1.12 1.18 1.17 CH2(q) 3.48 3.41 3.38 3.26 3.42 3.49 3.56 二甲基甲酰胺CH 8.02 7.96 7.95 7.63 7.92 7.79 7.92CH3 2.96 2.94 2.89 2.36 2.89 2.993.01CH3 2.88 2.78 2.73 1.86 2.77 2.862.85二甲基亚砜 2.62 2.52 2.54 1.68 2.50 2.65 二氧杂环 3.71 3.59 3.57 3.35 3.60 3.66乙醇2.713.75CH3(t) 1.25 1.12 1.06 0.96 1.12 1.19 1.17 CH2(q) 3.72 3.57 3.44 3.34 3.54 3.60 3.65 OH(s) 1.32 3.39 3.63 — 2.47 乙酸乙酯CH3CO 2.05 1.97 1.99 1.65 1.97 2.01 2.07 OCH2(q) 4.12 4.05 4.03 3.89 4.06 4.09 4.14 CH3(t) 1.26 1.20 1.17 0.92 1.20 1.24 1.24甲乙酮CH3CO 2.14 2.07 2.07 1.58 2.06 2.12 2.19 CH2(q) 2.46 2.45 2.43 1.81 2.43 2.50 3.18 CH3(t) 1.06 0.96 0.91 0.85 0.96 1.01 1.26乙二醇 3.76 3.28 3.34 3.41 3.51 3.59 3.65润滑脂CH3(m)0.86 0.87 —0.920.86 0.88CH2(br) 1.26 1.29 — 1.36 1.27 1.29 正己烷CH3(t)0.88 0.88 0.860.89 0.89 0.90CH2 (m) 1.26 1.28 1.25 1.24 1.28 1.29甲醇CH3 3.49 3.31 3.16 3.07 3.28 3.34 3.34OH 1.09 3.12 4.01 2.16正戊烷CH3(t)0.88 0.88 0.860.87 0.89 0.90CH2(m) 1.27 1.27 1.27 1.23 1.29 1.29异丙醇CH3(d) 1.22 1.10 1.04 0.95 1.09 1.50 1.17CH 4.04 3.90 3.78 3.67 3.87 3.92 4.02硅脂0.07 0.13 —0.29 0.08 0.10四氢呋喃CH2 1.85 1.79 1.76 1.40 1.80 1.87 1.88CH20 3.76 3.63 3.60 3.57 3.64 3.71 3.74甲苯CH3 2.36 2.32 2.30 2.11 2.33 2.32 —CH( o/p)7.17 7.20 7.18 7.02 7.30 7.16 —CH( m)7.25 7.20 7.25 7.13 7.30 7.16 —三乙基胺CH3 1.03 0.96 0.93 0.96 0.96 1.05 0.99CH2 : 2.53 2.45 2.43 2.40 2.45 2.58 2.57石油醚0.5-1.5 0.6-1.9 ——（注：专业文档是经验性极强的领域，无法思考和涵盖全面，素材和资料部分来自网络，供参考。