2010年最新NMR中残留溶剂或者杂质的标准化学位移

pubs.acs.org/OrganometallicsrXXXX American Chemical Society Organometallics XXXX, XXX, 000–000 A DOI: 10.1021/om100106e NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist Gregory R. Fulmer,*,† Alexander J. M. Miller,‡ Nathaniel H. Sherden,‡ Hugo E. Gottlieb,§ Abraham Nudelman,§ Brian M. Stoltz,‡ John E. Bercaw,‡ and Karen 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 and Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, and §Department of Chemistry, Bar Ilan University, Ramat Gan 52900, Israel Received February 11, 2010 Tables 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-d8, toluene-d8, dichloromethane-d2, chlorobenzene-d5, and 2,2,2-trifluoroethanol-d3) 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 ofmost every chemist whosework relies heavily on using NMR spectroscopy1 is NMR Chemi- cal Shifts of Common Laboratory Solvents as Trace Impu- rities by Gottlieb, Kotlyar, and Nudelman.2 By 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,3 the chemical shifts of impurities in a number of NMR solvents often used by organometallic chemists were not included. Tetrahydrofuran-d8 (THF-d8), toluene-d8, dichloromethane-d2 (CD2Cl2), chlorobenzene-d5 (C6D5Cl), and 2,2,2-trifluoroethanol-d3 (TFE-d3) 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 Section All deuterated solvents were obtained commercially through Cambridge Isotope Laboratories, Inc. NMR spectra were recorded at 298 K using 300, 500, or 600 MHz spectrometers (13C{1H} NMR frequencies of 75.5, 126, or 151 MHz, res- pectively). Adopting the previously reported strategy,2 standard 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@ u.washington.edu. (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, A. J. Org. Chem. 1997, 62, 7512. (3) According toACSPublications as ofDecember 2009 (http://pubs. acs.org/), Gottlieb et al.’s publication2 is the most downloaded Journal of Organic Chemistry article over the preceding 12 months. B Organometallics, Vol. XXX, No. XX, XXXX Fulmer et al. Table 1. 1H NMR Dataa proton mult THF-d8 CD2Cl2 CDCl3 toluene-d8 C6D6 C6D5Cl (CD3)2CO (CD3)2SO CD3CN TFE-d3 CD3OD D2O solvent residual signals 1.72 5.32 7.26 2.08 7.16 6.96 2.05 2.50 1.94 5.02 3.31 4.79 3.58 6.97 6.99 3.88 7.01 7.14 7.09 water OH s 2.46 1.52 1.56 0.43 0.40 1.03 2.84b 3.33b 2.13 3.66 4.87 acetic acid CH3 s 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 CH3 s 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 CH3 s 1.95 1.97 2.10 0.69 0.58 1.21 2.05 2.07 1.96 1.95 2.03 2.06 benzene CH s 7.31 7.35 7.36 7.12 7.15 7.20 7.36 7.37 7.37 7.36 7.33 tert -butyl alcohol CH3 s 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 sc 3.16 0.58 0.63 1.30 4.19 2.18 2.20 chloroform CH s 7.89 7.32 7.26 6.10 6.15 6.74 8.02 8.32 7.58 7.33 7.90 18-crown-6 CH2 s 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 CH2 s 1.44 1.44 1.43 1.40 1.40 1.37 1.43 1.40 1.44 1.47 1.45 1,2-dichloroethane CH2 s 3.77 3.76 3.73 2.91 2.90 3.26 3.87 3.90 3.81 3.71 3.78 dichloromethane CH2 s 5.51 5.33 5.30 4.32 4.27 4.77 5.63 5.76 5.44 5.24 5.49 diethyl ether CH3 t, 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 CH2 q, 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 CH2 m 3.43 3.57 3.65 3.43 3.46 3.49 3.56 3.51 3.53 3.67 3.61 3.67 CH2 m 3.53 3.50 3.57 3.31 3.34 3.37 3.47 3.38 3.45 3.62 3.58 3.61 OCH3 s 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 s 7.91 7.96 8.02 7.57 7.63 7.73 7.96 7.95 7.92 7.86 7.97 7.92 CH3 s 2.88 2.91 2.96 2.37 2.36 2.51 2.94 2.89 2.89 2.98 2.99 3.01 CH3 s 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 CH2 s 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 CH3 s 3.28 3.34 3.40 3.12 3.12 3.17 3.28 3.24 3.28 3.40 3.35 3.37 CH2 s 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 CH3 s 0.85 0.85 0.87 0.81 0.80 0.79 0.83 0.82 0.85 0.85 0.85 0.82 ethanol CH3 t, 7 1.10 1.19 1.25 0.97 0.96 1.06 1.12 1.06 1.12 1.22 1.19 1.17 CH2 q, 7 d 3.51 3.66 3.72 3.36 3.34 3.51 3.57 3.44 3.54 3.71 3.60 3.65 OH sc,d 3.30 1.33 1.32 0.83 0.50 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 2.07 CH2CH3 q, 7 4.04 4.08 4.12 3.87 3.89 3.96 4.05 4.03 4.06 4.14 4.09 4.14 CH2CH3 t, 7 1.19 1.23 1.26 0.94 0.92 1.04 1.20 1.17 1.20 1.26 1.24 1.24 ethylene CH2 s 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 CH2 s 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 greasef CH3 m 0.85-0.91 0.84-0.90 0.84-0.87 0.89-0.96 0.90-0.98 0.86-0.92 0.90 0.82-0.88 0.88-0.94 0.86-0.93 CH2 br s 1.29 1.27 1.25 1.33 1.32 1.30 1.29 1.24 1.33 1.29 hexamethylbenzene CH3 s 2.18 2.20 2.24 2.10 2.13 2.10 2.17 2.14 2.19 2.24 2.19 n-hexane CH3 t, 7 0.89 0.89 0.88 0.88 0.89 0.85 0.88 0.86 0.89 0.91 0.90 CH2 m 1.29 1.27 1.26 1.22 1.24 1.19 1.28 1.25 1.28 1.31 1.29 HMDSO CH3 s 0.07 0.07 0.07 0.10 0.12 0.10 0.07 0.06 0.07 0.08 0.07 0.28 HMPA CH3 d,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 H2 s 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) s 7.48 7.63 7.67 7.30 7.33 7.53 7.62 7.63 7.57 7.61 7.67 7.78 CH(4,5) s 6.94 7.07 7.10 6.86 6.90 7.01 7.04 7.01 7.01 7.03 7.05 7.14 methane CH4 s 0.19 0.21 0.22 0.17 0.16 0.15 0.17 0.20 0.20 0.18 0.20 0.18 methanol CH3 s 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 sc,g 3.02 1.09 1.09 1.30 3.12 4.01 2.16 nitromethane CH3 s 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 CH3 t, 7 0.89 0.89 0.88 0.87 0.87 0.84 0.88 0.86 0.89 0.90 0.90 CH2 m 1.31 1.30 1.27 1.25 1.23 1.23 1.27 1.27 1.29 1.33 1.29 propane CH3 t, 7.3 0.90 0.90 0.90 0.89 0.86 0.84 0.88 0.87 0.90 0.90 0.91 0.88 CH2 sept, 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 CH3 d, 6 1.08 1.17 1.22 0.95 0.95 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 CH3 dt, 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 4.95 CH2(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 5.06 CH 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) m 8.54 8.59 8.62 8.47 8.53 8.51 8.58 8.58 8.57 8.45 8.53 8.52 CH(3,5) m 7.25 7.28 7.29 6.67 6.66 6.90 7.35 7.39 7.33 7.40 7.44 7.45 CH(4) m 7.65 7.68 7.68 6.99 6.98 7.25 7.76 7.79 7.73 7.82 7.85 7.87 pyrrole NH br t 9.96 8.69 8.40 7.71 7.80 8.61 10.02 10.75 9.27 CH(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 6.93 CH(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 pyrrolidineh 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 CH3 s 0.11 0.09 0.07 0.26 0.29 0.14 0.13 -0.06 0.08 0.16 0.10 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 CH3 s 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) m 7.10 7.15 7.17 6.96-7.01 7.02 7.01-7.08 7.10-7.20 7.18 7.10-7.30 7.10-7.30 7.16 CH(3,5) m 7.19 7.24 7.25 7.09 7.13 7.10-7.17 7.10-7.20 7.25 7.10-7.30 7.10-7.30 7.16 triethylamine CH3 t, 7 0.97 0.99 1.03 0.95 0.96 0.93 0.96 0.93 0.96 1.31 1.05 0.99 CH2 q,7 2.46 2.48 2.53 2.39 2.40 2.39 2.45 2.43 2.45 3.12 2.58 2.57 aExcept for the compounds in solutions 8-10, 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 ref 2. bA signal for HDO is also observed in (CD3)2SO (3.30 ppm) and (CD3)2CO (2.81 ppm), often seen as a 1:1:1 triplet ( 2JH,D = 1 Hz). cNot all OH signals were observable. d In some solvents, the coupling interaction between the CH2 and the OH protons may be observed (J=5Hz). e In CD3CN, the OH proton was seen as a multiplet at 2.69 ppm, as well as extra coupling to the CH2 resonance. fApiezon brandH grease. g In some solvents, a coupling interaction between the CH3 and the OH protons may be observed (J= 5.5 Hz). hPyrrolidine was observed to react with (CD3)2CO. Article Organometallics, Vol. XXX, No. XX, XXXX C Table 2. 13C{1H} NMR Dataa carbon THF-d8 CD2Cl2 CDCl3 toluene- d8 C6D6 C6D5Cl (CD3)2CO (CD3)2SO CD3CN TFE-d3 CD3OD D2O solvent signals 67.21 53.84 77.16 137.48 128.06 134.19 29.84 39.52 1.32 61.50 49.00 25.31 128.87 129.26 206.26 118.26 126.28 127.96 128.25 125.13 125.96 20.43 acetic acid CO 171.69 175.85 175.99 175.30 175.82 175.67 172.31 171.93 173.21 177.96 175.11 177.21 CH3 20.13 20.91 20.81 20.27 20.37 20.40 20.51 20.95 20.73 20.91 20.56 21.03 acetone CO 204.19 206.78 207.07 204.00 204.43 204.83 205.87 206.31 207.43 32.35 209.67 215.94 CH3 30.17 31.00 30.92 30.03 30.14 30.12 30.60 30.56 30.91 214.98 30.67 30.89 acetonitrile CN 116.79 116.92 116.43 115.76 116.02 115.93 117.60 117.91 118.26 118.95 118.06 119.68 CH3 0.45 2.03 1.89 0.03 0.20 0.63 1.12 1.03 1.79 1.00 0.85 1.47 benzene CH 128.84 128.68 128.37 128.57 128.62 128.38 129.15 128.30 129.32 129.84 129.34 tert -butyl alcohol (CH3)3C 67.50 69.11 69.15 68.12 68.19 68.19 68.13 66.88 68.74 72.35 69.40 70.36 (CH3)3C 30.57 31.46 31.25 30.49 30.47 31.13 30.72 30.38 30.68 31.07 30.91 30.29 carbon dioxide CO2 125.69 125.26 124.99 124.86 124.76 126.08 125.81 124.21 125.89 126.92 126.31 carbon disulfide CS2 193.37 192.95 192.83 192.71 192.69 192.49 193.58 192.63 193.60 196.26 193.82 197.25 carbon tetrachloride CCl4 96.89 96.52 96.34 96.57 96.44 96.38 96.65 95.44 96.68 97.74 97.21 96.73 chloroform CH 79.24 77.99 77.36 77.89 77.79 77.67 79.19 79.16 79.17 78.83 79.44 18-crown-6 CH2 71.34 70.47 70.55 70.86 70.59 70.55 71.25 69.85 71.22 70.80 71.47 70.14 cyclohexane CH2 27.58 27.38 26.94 27.31 27.23 26.99 27.51 26.33 27.63 28.34 27.96 1,2-dichloroethane CH2 44.64 44.35 43.50 43.40 43.59 43.60 45.25 45.02 45.54 45.28 45.11 dichloromethane CH2 54.67 54.24 53.52 53.47 53.46 53.54 54.95 54.84 55.32 54.46 54.78 diethyl ether CH3 15.49 15.44 15.20 15.47 15.46 15.35 15.78 15.12 15.63 15.33 15.46 14.77 CH2 66.14 66.11 65.91 65.94 65.94 65.79 66.12 62.05 66.32 67.55 66.88 66.42 diglyme CH3 58.72 58.95 59.01 58.62 58.66 58.42 58.77 57.98 58.90 59.40 59.06 58.67 CH2 71.17 70.70 70.51 70.92 70.87 70.56 71.03 69.54 70.99 73.05 71.33 70.05 CH2 72.72 72.25 71.90 72.39 72.35 72.07 72.63 71.25 72.63 71.33 72.92 71.63 dimethylformamide CH 161.96 162.57 162.62 161.93 162.13 162.01 162.79 162.29 163.31 166.01 164.73 165.53 CH3 35.65 36.56 36.50 35.22 35.25 35.45 36.15 35.73 36.57 37.76 36.89 37.54 CH3 30.70 31.39 31.45 30.64 30.72 30.71 31.03 30.73 31.32 30.96 31.61 32.03 1,4-dioxane CH2 67.65 67.47 67.14 67.17 67.16 66.95 67.60 66.36 67.72 68.52 68.11 67.19 DME CH3 58.72 59.02 59.08 58.63 58.68 58.31 58.45 58.03 58.89 59.52 59.06 58.67 CH2 72.58 72.24 71.84 72.25 72.21 71.81 72.47 71.17 72.47 72.87 72.72 71.49 ethane CH3 6.79 6.91 6.89 6.94 6.96 6.91 6.88 6.61 6.99 7.01 6.98 ethanol CH3 18.90 18.69 18.41 18.78 18.72 18.55 18.89 18.51 18.80 18.11 18.40 17.47 CH2 57.60 58.57 58.28 57.81 57.86 57.63 57.72 56.07 57.96 59.68 58.26 58.05 ethyl acetate CH3CO 20.45 21.15 21.04 20.46 20.56 20.50 20.83 20.68 21.16 21.18 20.88 21.15 CO 170.32 171.24 171.36 170.02 170.44 170.20 170.96 170.31 171.68 175.55 172.89 175.26 CH2 60.30 60.63 60.49 60.08 60.21 60.06 60.56 59.74 60.98 62.70 61.50 62.32 CH3 14.37 14.37 14.19 14.23 14.19 14.07 14.50 14.40 14.54 14.36 14.49 13.92 ethylene CH2 123.09 123.20 123.13 122.92 122.96 122.95 123.47 123.52 123.69 124.08 123.46 ethylene glycol CH2 64.35 64.08 63.79 64.29 64.34 64.03 64.26 62.76 64.22 64.87 64.30 63.17 H greaseb CH2 30.45 30.14 29.71 30.31 30.22 30.11 hexamethylbenzene C 131.88 132.09 132.21 131.72 131.79 131.54 132.22 131.10 132.61 134.04 132.53 CH3 16.71 16.93 16.98 16.84 16.95 16.68 16.86 16.60 16.94 17.04 16.90 n-hexane CH3 14.22 14.28 14.14 14.34 14.32 14.18 14.34 13.88 14.43 14.63 14.45 CH2(2,5) 23.33 23.07 22.70 23.12 23.04 22.86 23.28 22.05 23.40 24.06 23.68 CH2(3,4) 32.34 32.01 31.64 32.06 31.96 31.77 32.30 30.95 32.36 33.17 32.73 HMDSO 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 HMPAc CH3 36.89 36.99 36.87 36.80 36.88 36.64 37.04 36.42 37.10 37.21 37.00 36.46 imidazole CH(2) 135.72 135.76 135.38 135.57 135.76 135.50 135.89 135.15 136.33 136.58 136.31 136.65 CH(4,5) 122.20 122.16 122.00 122.13 122.16 121.96 122.31 121.55 122.78 122.93 122.60 122.43 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 CH3 49.64 50.45 50.41 49.90 49.97 49.66 49.77 48.59 49.90 50.67 49.86 49.50 d nitromethane CH3 62.49 63.03 62.50 61.14 61.16 61.68 63.21 63.28 63.66 63.17 63.08 63.22 n-pentane CH3 14.18 14.24 14.08 14.27 14.25 14.10 14.29 13.28 14.37 14.54 14.39 CH2(2,4) 23.00 22.77 22.38 22.79 22.72 22.54 22.98 21.70 23.08 23.75 23.38 CH2(3) 34.87 34.57 34.16 34.54 34.45 34.26 34.83 33.48 34.89 35.76 35.30 propane CH3 16.60 16.63 16.63 16.65 16.66 16.56 16.68 16.34 16.73 16.93 16.80 CH2 16.82 16.63 16.37 16.63 16.60 16.48 16.78 15.67 16.91 17.46 17.19 2-propanol CH3 25.70 25.43 25.14 25.24 25.18 25.14 25.67 25.43 25.55 25.21 25.27 24.38 CH 66.14 64.67 64.50 64.12 64.23 64.18 63.85 64.92 64.30 66.69 64.71 64.88 propylene CH3 19.27 19.47 19.50 19.32 19.38 19.32 19.42 19.20 19.48 19.63 19.50 CH2 115.74 115.70 115.74 115.89 115.92 115.86 116.03 116.07 116.12 116.38 116.04 CH 134.02 134.21 133.91 133.61 133.69 133.57 134.34 133.55 134.78 136.00 134.61 pyridine CH(2,6) 150.57 150.27 149.90 150.25 150.27 149.93 150.67 149.58 150.76 149.76 150.07 149.18 CH(3,5) 124.08 124.06 123.75 123.46 123.58 123.49 124.57 123.84 127.76 126.27 125.53 125.12 CH(4) 135.99 136.16 135.96 135.17 135.28 135.32 136.56 136.05 136.89 139.62 138.35 138.27 pyrrole CH(2,5) 118.03 117.93 117.77 117.61 117.78 117.65 117.98 117.32 118.47 119.61 118.28 119.06 CH(3,4) 107.74 108.02 107.98 108.15 108.21 108.03 108.04 107.07 108.31 108.85 108.11 107.83 pyrrolidinee CH2(2,5) 45.82 47.02 46.93 47.12 46.86 46.75 46.51 47.57 47.43 47.23 46.83 CH2(3,4) 26.17 25.83 25.56 25.75 25.65 25.59 25.26 26.34 25.73 26.29 25.86 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) 68.03 68.16 67.97 67.75 67.80 67.64 68.07 67.03 68.33 69.53 68.83 68.68 CH2(3,4) 26.19 25.98 25.62 25.79 25.72 25.68 26.15 25.14 26.27 26.69 26.48 25.67 toluene CH3 21.29 21.53 21.46 21.37 21.10 21.23 21.46 20.99 21.50 21.62 21.50 C(1) 138.24 138.36 137.89 137.84 137.91 137.65 138.48 137.35 138.90 139.92 138.85 CH(2,6) 129.47 129.35 129.07 129.33 129.33 129.12 129.76 128.88 129.94 130.58 129.91 CH(3,5) 128.71 128.54 128.26 128.51 128.56 128.31 129.03 128.18 129.23 129.79 129.20 CH(4) 125.84 125.62 125.33 125.66 125.68 125.43 126.12 125.29 126.28 126.82 126.29 triethylamine CH3 12.51 12.12 11.61 12.39 12.35 11.87 12.49 11.74 12.38 9.51 11.09 9.07 CH2 47.18 46.75 46.25 46.82 46.77 46.36 47.07 45.74 47.10 48.45 46.96 47.19 aExcept for the compounds in solutions 8-10, 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 ref 2. bApiezon brand H grease. cPhosphorus coupling was observed (2JPC = 3 Hz). d Internal reference; see text. ePyrrolidine was observed to react with (CD3)2CO. D Organometallics, Vol. XXX, No. XX, XXXX Fulmer et al. 1,2-dimethoxyethane (DME), nitromethane, poly(dimethylsiloxane) (silicone grease), triethylamine; (solution 7) diglyme, dimethyl- acetamide, ethylene glycol, ethyl methyl ketone; (solution 8) allyl acetate, 2,6-di-tert-butyl-4-methoxyphenol (BHA), long- chain, linear aliphatic hydrocarbons from pump oil;4 (solu- tion 9) benzaldehyde, carbon disulfide, carbon tetrachloride, cyclohexanone, dimethyl malonate, furan, Apiezon H grease (H grease); (solution 10) 18-crown-6, diallyl carbonate, dimethyl carbonate, hexamethyldisiloxane (HMDSO), imidazole, pyrrole, pyrrolidine.5 In the case of TFE-d3, nitromethane was omitted from solution 6 and run separately, since the protons of nitro- methane exchange with deuterium from TFE-d3 in the presence of triethylamine. In the case of (CD3)2CO, pyrrolidine was omitted from solution 10, 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 by 1H NMR spectroscopy, solvent residual signals6 and chemical shifts for H2O 7 for each NMR solvent were refer- enced against tetramethylsilane (TMS, δ 0 ppm) and reported. Before collecting 13C{1H} NMR spectral data, solvent signals6 were recorded with reference to the signal of a TMS internal standard. For D2O,