Analyses of the structural and electronic properties of NHCs with bicyclic architectures - Ando et al. - Unknown - Unknown

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SupportingInformationAnalysesofthestructuralandelectronicpropertiesofNHCswithbicyclicarchitecturesShinAndo*,MioOtsuka,andTadaoIshizuka*FacultyofLifeSciences,KumamotoUniversity,5-1Oe-honmachiChuo-ku,Kumamoto862-0973,JapanE-mail:ando@gpo.kumamoto-u.ac.jp(S.A.),tstone@gpo.kumamoto-u.ac.jp(T.I.)TableofContents1.1Hand13CNMRspectraofnovelcompounds··········································S2–S172.IRspectraofthe[IrCl(CO)2(NHC)]complexes······································S18–S193.1Hspectraofthecrudeproductsfromtheallylicarylations································S204.Crystallographicdataofcomplex13··························································S215.Crystallographicdataofcomplex14··························································S226.Crystallographicdataofcomplex20··························································S237.Crystallographicdataofcomplex23··························································S248.StructuralanalysesofNHCswithSambVca2.1program··························S25–S319.References························································································S32S1

1CurrentDataParametersNAME3239.0927.2547.2487.2477.2447.2407.2347.2287.2247.2217.2197.2134.9304.9274.9243.8803.8693.8583.8473.8353.8152.9242.7742.6602.1012.0972.0952.0832.0802.0781.8501.8491.8471.8341.8321.8301.6021.3971.386EXPNO1PROCNO1F2-AcquisitionParametersDate_20191206Time18.58INSTRUMav600PROBHD5mmPABBOBB-3.8803.8693.8583.8473.8353.8151.8501.8491.8471.8341.8321.8301.3971.3861.3591.348PULPROGzg30TD65536SOLVENTCDCl3NS16DS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG362DW40.400usecDE6.50usecTE300.0KD11.00000000sec3.85ppm1.84ppmppmTD017.2547.2487.2477.2447.2407.2347.2287.2247.219========CHANNELf1========NUC11HP115.00usec4.9304.9274.924PL1-2.00dB2.1012.0972.0952.0832.0802.078SFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300164MHzWDWEMSSB0LB0.30HzGB0PC1.007.24ppmppm2.10ppmi-PrNClNi-Pr109876543210ppm1.004.191.932.092.030.740.130.161.031.066.886.366.34FigureS1.1HNMRspectrumofcompound10(600MHz,CDCl3,300K)154.73141.94127.59123.7766.0050.7950.1948.5547.3321.2520.93CurrentDataParametersNAMEBCPSIiPrClEXPNO2PROCNO1F2-AcquisitionParametersDate_20200408i-PrTime14.29NINSTRUMav600NPROBHD5mmPABBOBB-ClPULPROGzgpg30TD143880i-PrSOLVENTCDCl3NS800DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG18390.4DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01CH3OH========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524915MHz200180160140120100806040200ppmWDWEMSSB0LB1.00HzGB0PC1.40FigureS2.13CNMRspectrumofcompound10(600MHz,CDCl3,300K)S2

2CurrentDataParameters8.8607.2457.2387.2347.2307.2227.2187.2157.2084.9914.9884.9843.8163.4283.4223.4163.4022.1262.1062.0762.0601.8771.8561.8391.7431.7371.7231.7171.6721.6511.6351.5301.5241.5101.5041.3511.3451.3401.3351.3291.3231.3181.3131.3081.2601.2391.217NAME406-1EXPNO1PROCNO1F2-AcquisitionParametersDate_20200520Time16.09INSTRUMav600PROBHD5mmPABBOBB-4.9914.9884.9842.1262.1062.0802.0762.0742.0632.0602.0571.5511.5451.5301.5241.5101.5041.3291.3231.3181.3131.2601.2441.2391.2331.217PULPROGzg30TD65536SOLVENTCDCl3NS16DS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG456.1DW40.400usecDE6.50usecppmppmppmppmppmppmTE300.0KD11.00000000secTD01========CHANNELf1========NUC11H7.2457.2387.2347.2307.2227.2187.2153.8163.4423.4363.4283.4223.4163.4083.4021.8771.8561.8391.7571.7431.7371.7231.7171.7021.6961.6721.6511.635P115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300127MHzWDWEMSSB0LB0.30HzGB0ppmppmppmppm1.75ppmppmPC1.00CyNClNCy109876543210ppm1.004.312.002.032.112.101.125.602.524.572.654.832.72FigureS3.1HNMRspectrumofcompound12(600MHz,CDCl3,300K)155.02141.69127.49123.6065.6357.4748.5047.1031.7331.0925.2725.0424.86CurrentDataParametersCyNAMEBCPSICy-ClNEXPNO2ClNPROCNO1CyF2-AcquisitionParametersDate_20200522Time9.59INSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS760DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG16384DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8525180MHzWDWEM200180160140120100806040200ppmSSB0LB1.00HzGB0PC1.40FigureS4.13CNMRspectrumofcompound12(600MHz,CDCl3,300K)S3

37.1907.1857.1817.1767.1517.1467.1427.1374.6674.6644.6613.9383.9263.9153.9043.8923.6392.0062.0041.9901.9881.7481.7461.7441.7321.7301.7271.3221.3111.2641.253CurrentDataParametersNAME2862.0062.0041.9901.9881.3221.3111.2641.253EXPNO11.7481.7461.7441.7321.7301.727PROCNO1F2-AcquisitionParametersDate_20191108Time10.07INSTRUMav600PROBHD5mmPABBOBB-PULPROGzg30TD65536SOLVENTCDCl3NS16DS2SWH12376.237Hz2.00ppm1.74ppm1.30ppmFIDRES0.188846HzAQ2.6476543secRG362DW40.400usecDE6.50usec4.6674.6644.661TE300.0K3.9383.9263.9153.9043.892D11.00000000sec7.1907.1857.1817.1767.1517.1467.1427.137TD01========CHANNELf1========NUC11HP115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300164MHz3.953.90ppmWDWEMppmppmSSB0LB0.30HzGB0PC1.00109876543210ppmNi-PrNAgCl1.971.912.011.962.131.000.998.741.546.446.37i-PrFigureS5.1HNMRspectrumofcomplex13(600MHz,CDCl3,300K)142.77126.78124.0366.3452.6149.4548.4522.8122.45CurrentDataParametersNAMESAp10_BCPSIiPr-Agi-PrEXPNO2NPROCNO1NAgClF2-AcquisitionParametersi-PrDate_20200514Time11.48INSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS800DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG16384DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524995MHzWDWEMSSB0LB1.00HzGB0PC1.40200180160140120100806040200ppmFigureS6.13CNMRspectrumofcomplex13(600MHz,CDCl3,300K)S4

47.1727.1677.1647.1637.1587.1397.1347.1307.1255.3084.6584.6554.6523.6353.4472.0111.8451.8301.8261.8081.8041.7111.6941.6911.6841.6701.6641.6281.5181.5121.4971.4911.3451.3241.3181.3121.3071.2961.2901.2841.2751.2681.2621.1521.1300.8910.879CurrentDataParameters4.6584.6554.6523.4673.4613.4543.4473.4413.4343.4272.0312.0111.5391.5331.5181.5121.4971.4911.4771.3451.3241.3181.3121.3071.2961.2901.1581.1521.1451.1361.1301.124NAME304-2EXPNO1PROCNO1F2-AcquisitionParametersDate_20191121Time17.48INSTRUMav600PROBHD5mmPABBOBB-PULPROGzg30TD65536SOLVENTCDCl3NS16ppm3.45ppmppmppmppm1.15ppmDS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG322.5DW40.400usec7.1727.1677.1647.1637.1587.1397.1347.1307.1251.9781.9761.9611.9601.8451.8301.8261.8081.6941.6911.6701.6641.6431.628DE6.50usecTE300.0KD11.00000000secTD01========CHANNELf1========NUC11HP115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768ppmppmppmppm1.70ppmppmSF599.9300126MHzWDWEMSSB0LB0.30HzCH2Cl2GB0PC1.00Cy109876543210ppmNNAgCl2.062.001.022.182.262.310.232.431.215.305.563.453.077.132.631.09CyFigureS7.1HNMRspectrumofcomplex14(600MHz,CDCl3,300K)142.75126.57123.9066.5960.7349.4547.9733.5133.0925.7025.6725.33CurrentDataParametersCyNAMEBCPSICy-Ag3NEXPNO2NPROCNO1AgClF2-AcquisitionParametersCyDate_20200601Time13.00INSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS760DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG18390.4DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8525180MHzWDWEM200180160140120100806040200ppmSSB0LB1.00HzGB0PC1.40FigureS8.13CNMRspectrumofcomplex14(600MHz,CDCl3,300K)S5

57.3207.3157.3117.3067.3007.2947.2917.2857.1887.1827.1797.1737.1687.1637.1597.1545.3094.5954.5934.5914.3834.3784.3734.1984.1964.1943.3552.0522.0482.0452.0392.0351.9731.9661.9621.9601.9561.9071.9021.8971.6181.6091.5991.5651.4261.4161.403CurrentDataParameters1.6181.6091.5991.4391.4261.4161.4031.392NAME3482.0522.0482.0452.0351.9731.9621.9601.956EXPNO17.1887.1827.1797.1737.1687.1637.1597.154PROCNO1F2-AcquisitionParametersDate_20200127Time15.38INSTRUMav600PROBHD5mmPABBOBB-PULPROGzg30TD65536SOLVENTCDCl3NS16DS2ppm2.0ppmppmppmSWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG362DW40.400usecDE6.50usec7.3207.3157.3117.3067.3007.2947.2917.2854.1984.1964.1944.5954.5934.5914.3834.3784.3731.9071.9021.897TE300.0KD11.00000000secTD01========CHANNELf1========NUC11HP115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300123MHzWDWEM7.327.30ppmppmppmppmppmSSB0LB0.30HzGB0PC1.00109876543210ppmMeNN4.554.350.132.092.002.066.492.242.232.182.502.300.34IrMeClFigureS9.1HNMRspectrumofcomplex19(600MHz,CDCl3,300K)208.48139.75138.52127.22126.90125.65125.1284.8968.5252.5846.1134.5733.3129.31MeNNCurrentDataParametersIrNAMEDHASIMe-IrMeEXPNO2ClPROCNO1F2-AcquisitionParametersDate_20200526Time8.46INSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS9600DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG18390.4DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524957MHzWDWEM200180160140120100806040200ppmSSB0LB1.00HzGB0PC1.40FigureS10.13CNMRspectrumofcomplex19(600MHz,CDCl3,300K)S6

67.2997.2937.2907.2847.2837.2777.2737.2687.1647.1597.1557.1527.1507.1477.1437.1385.3865.3755.3635.3024.5814.4014.3994.3974.3354.3304.3252.1012.0962.0912.0462.0361.9691.9591.6021.5921.5881.5851.5781.5651.5431.5311.4431.4321.4301.4191.3121.301CurrentDataParametersNAMESAp10_DHASIiPr-IrEXPNO17.2907.2847.2837.2737.2685.3985.3865.3755.3635.3524.4014.3994.3972.0962.0912.0532.0492.0462.0402.0362.0261.9651.9591.9521.5651.5431.5311.3121.301PROCNO1F2-AcquisitionParametersDate_20191209Time9.45INSTRUMav600PROBHD5mmPABBOBB-PULPROGzg30TD65536SOLVENTCDCl3NS16DS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543sec7.30ppm5.4ppmppm2.102.05ppmppmppmppmRG362DW40.400usecDE6.50usecTE300.0KD11.00000000sec1.4431.4321.4301.419TD017.1647.1597.1557.1527.1504.5814.3354.3304.3251.5851.5651.5431.531========CHANNELf1========NUC11HP115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300164MHzWDWEMSSB0LB0.30HzGB0ppmPC1.00ppmppmppm1.6ppmi-Pr109876543210ppmNNIr4.564.042.060.122.031.972.042.082.012.052.746.372.226.00i-PrClFigureS11.1HNMRspectrumofcomplex20(600MHz,CDCl3,300K)212.66140.73139.02127.10126.55126.25125.0183.8564.0153.1052.5549.0533.3529.3323.4020.37i-PrNNCurrentDataParametersIrNAMEDHASIiPr-Ir2i-PrEXPNO2PROCNO1ClF2-AcquisitionParametersDate_20200424Time8.53INSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS9800DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG16384DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524964MHz200180160140120100806040200ppmWDWEMSSB0LB1.00HzGB0PC1.40FigureS12.13CNMRspectrumofcomplex20(600MHz,CDCl3,300K)S7

77.2997.2937.2907.2847.2567.2507.1557.1507.1467.1417.1367.1317.1277.1224.9834.5924.3652.1222.1022.0712.0662.0621.9971.9731.8821.8611.8561.8401.7541.7321.6131.6031.5991.5901.5801.5221.5181.5141.5061.4921.4701.4571.4461.4331.2301.2080.886CurrentDataParametersNAME331-1EXPNO11.6131.6031.5991.5901.5801.2301.208PROCNO17.1557.1507.1467.1417.1367.1317.1272.1222.1021.5221.5181.4701.4571.4461.433F2-AcquisitionParametersDate_20191216Time13.25INSTRUMav600PROBHD5mmPABBOBB-PULPROGzg30TD65536SOLVENTCDCl3NS16DS2SWH12376.237Hzppmppm1.5ppmppmFIDRES0.188846HzAQ2.6476543sec7.14ppmRG362DW40.400usecDE6.50usecTE300.0K5.0034.9984.9834.9694.9642.0712.0662.0621.8821.8611.8401.7541.732D11.00000000secTD017.2997.2937.2907.284========CHANNELf1========NUC11HP115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI327685.00ppmppmppmSF599.9300164MHzWDWEMSSB0LB0.30HzGB0ppmPC1.00109876543210ppmCyNNIr2.421.994.002.082.124.162.252.429.163.010.62Cy17.22ClFigureS13.1HNMRspectrumofcomplex21(600MHz,CDCl3,300K)212.72140.76139.12127.03126.56126.15125.0083.4264.8161.1652.6949.1234.7133.5731.2029.4927.0026.0925.95CyNNCurrentDataParametersIrNAMEDHASICy-IrCyEXPNO2PROCNO1ClF2-AcquisitionParametersDate_20200512Time8.51INSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS9800DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG16384DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524951MHz200180160140120100806040200ppmWDWEMSSB0LB1.00HzGB0PC1.40FigureS14.13CNMRspectrumofcomplex21(600MHz,CDCl3,300K)S8

8CurrentDataParametersNAME3617.2187.2137.2097.2047.1197.1147.1107.1054.4494.4464.4424.3224.3174.3123.6073.6043.6013.2272.0182.0112.0042.0021.9951.9891.9821.9781.9701.9661.9391.9361.9331.9231.9191.9161.9001.6681.6651.6631.651EXPNO1PROCNO1F2-AcquisitionParametersDate_20200210Time10.15INSTRUMav6004.4494.4464.4424.3224.3174.312PROBHD5mmPABBOBB-PULPROGzg307.1197.1147.1107.1053.6073.6043.6011.6681.6651.6631.6511.6491.6471.3961.3831.3731.3661.362TD65536SOLVENTCDCl3NS16DS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG322.5DW40.400usecDE6.50usecppmppm1.4ppmTE300.0KppmppmppmD11.00000000secTD01========CHANNELf1========NUC11H7.2187.2137.2097.2041.9391.9361.9331.9231.9191.916P115.00usec2.0042.0021.9951.9891.9821.978PL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300187MHzWDWEMSSB0LB0.30HzGB0PC1.00ppm2.00ppm1.94ppmMeNNIrMeCl109876543210ppm1.941.931.991.961.945.832.011.912.991.002.03FigureS15.1HNMRspectrumofcomplex22(600MHz,CDCl3,300K)206.51142.89126.67122.8284.1169.8852.0647.8147.3635.0233.1429.12MeNNIrCurrentDataParametersMeNAMEBCPSIMe-IrEXPNO2ClPROCNO1F2-AcquisitionParametersDate_20200529Time8.38INSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS9600DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG18390.4DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzEt2OEt2OF2-ProcessingparametersSI32768SF150.8524987MHz200180160140120100806040200ppmWDWEMSSB0LB1.00HzGB0PC1.40FigureS16.13CNMRspectrumofcomplex22(600MHz,CDCl3,300K)S9

97.1997.1947.1907.1857.1057.1007.0967.0915.2115.2005.1885.1775.1664.6224.6184.6154.2974.2924.2873.5573.5543.5512.0182.0081.9371.9181.7321.7291.7271.7151.7131.7111.5511.3901.3791.2951.284CurrentDataParameters3.5573.5543.551NAME3452.0182.0081.9371.9181.2951.2841.3901.379EXPNO1PROCNO1F2-AcquisitionParametersDate_20200121Time11.10INSTRUMav600PROBHD5mmPABBOBB-PULPROGzg30TD65536SOLVENTCDCl3NS16DS2SWH12376.237HzppmppmppmFIDRES0.188846HzppmppmAQ2.6476543secRG362DW40.400usecDE6.50usec4.6224.6184.615TE300.0K7.1997.1947.1907.1857.1057.1007.0967.0915.2115.2005.1885.1775.1664.2974.2924.287D11.00000000sec1.7321.7291.7271.7151.713TD01========CHANNELf1========NUC11HP115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300137MHzWDWEMppmppmSSB05.20ppmppmppmppmLB0.30HzGB0PC1.00109876543210ppmi-PrNNIr1.982.022.052.042.002.042.044.691.006.976.23i-PrClFigureS17.1HNMRspectrumofcomplex23(600MHz,CDCl3,300K)210.26143.81125.98124.3683.4764.2552.7751.9250.0048.8333.3729.3122.5920.75i-PrNNIrCurrentDataParametersi-PrNAMEBCPSIiPr-IrClEXPNO2PROCNO1F2-AcquisitionParametersDate_20200428Time8.53INSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS9800DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG18390.4DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524962MHz200180160140120100806040200ppmWDWEMSSB0LB1.00HzGB0PC1.40FigureS18.13CNMRspectrumofcomplex23(600MHz,CDCl3,300K)S10

107.1827.1767.1737.1677.0917.0867.0837.0774.6034.5994.5964.3294.3244.3193.5373.5333.5302.0351.9861.9831.9681.9651.9171.9051.9021.8861.8081.6831.6811.6651.6211.6151.6011.5951.5811.4501.4371.4321.4201.4171.4101.3991.3701.3491.4501.4371.4321.4201.4171.4101.370CurrentDataParameters7.0917.0867.0837.0771.6831.6811.6651.6011.5951.581NAME342-14.6034.5994.5961.9171.9051.9021.8861.1441.1381.1321.1221.1161.110EXPNO1PROCNO1F2-AcquisitionParametersDate_20200115Time17.53INSTRUMav600PROBHD5mmPABBOBB-PULPROGzg30TD65536SOLVENTCDCl3NS16ppmppmppmppm1.51.4ppm1.15ppmDS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG2567.1827.1767.1737.1673.5373.5333.530DW40.400usec4.8024.7884.7824.7774.763DE6.50usec4.3294.3244.3192.0351.9861.9831.9781.9681.9651.6831.6811.665TE300.0K1.8081.7981.792D11.00000000secTD01========CHANNELf1========NUC11HP115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768ppm4.80ppmppmppmppmppmppmSF599.9300141MHzWDWEMSSB0LB0.30HzGB0PC1.00109876543210ppmCyNNIr-0.002.002.032.052.022.056.147.432.153.103.468.402.08CyClFigureS19.1HNMRspectrumofcomplex24(600MHz,CDCl3,300K)210.16143.93125.86124.4683.0965.2360.1652.3550.0348.6133.7833.5831.0629.4926.6725.9225.86CyNNCurrentDataParametersIrNAMEBCPSICy-IrCyEXPNO2ClPROCNO1F2-AcquisitionParametersDate_20200513Time8.49INSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS9800DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG18390.4DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524960MHz200180160140120100806040200ppmWDWEMSSB0LB1.00HzGB0PC1.40FigureS20.13CNMRspectrumofcomplex24(600MHz,CDCl3,300K)S11

11CurrentDataParametersNAME3517.3607.3557.3517.3467.2237.2187.2137.2097.2045.3104.6724.2924.2904.2873.2481.5571.263EXPNO1PROCNO1F2-AcquisitionParametersDate_20200128Time15.37INSTRUMav600PROBHD5mmPABBOBB-PULPROGzg307.2237.2187.2137.2097.204TD65536SOLVENTCDCl3NS16DS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG362DW40.400usec4.2924.2904.287DE6.50usecTE300.0KD11.00000000secTD01ppm========CHANNELf1========NUC11HP115.00usecPL1-2.00dBSFO1599.9337048MHz7.3607.3557.3517.346F2-ProcessingparametersSI32768SF599.9300119MHzWDWEMppmSSB0LB0.30HzGB0PC1.00ppmMeNCONIrMeCO109876543210ppmCl3.893.711.002.072.156.2716.87FigureS21.1HNMRspectrumofcomplex25(600MHz,CDCl3,300K)199.85181.79166.64139.22137.65127.59127.48125.48125.2168.6845.8434.92CurrentDataParametersNAMEDHASIMe-COEXPNO2PROCNO1MeF2-AcquisitionParametersNCODate_20200421NTime8.46IrINSTRUMav600PROBHD5mmPABBOBB-MeCOPULPROGzgpg30ClTD143880SOLVENTCDCl3NS9800DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG18390.4DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524960MHz200180160140120100806040200ppmWDWEMSSB0LB1.00HzGB0PC1.40FigureS22.13CNMRspectrumofcomplex25(600MHz,CDCl3,300K)S12

127.3367.3317.3277.3227.3177.1927.1907.1867.1857.1837.1817.1777.1765.3104.9534.9414.9304.9184.9074.8954.8834.6324.4904.4874.4861.5561.4671.4551.3711.360CurrentDataParametersNAME349EXPNO17.1927.1907.1867.1857.1837.1777.176PROCNO11.4671.4551.3711.360F2-AcquisitionParametersDate_20200128Time15.26INSTRUMav600PROBHD5mmPABBOBB-PULPROGzg30TD65536SOLVENTCDCl3NS16DS2SWH12376.237Hzppm1.4ppmFIDRES0.188846HzAQ2.6476543secRG362DW40.400usecDE6.50usec7.3367.3317.3277.3227.3174.9534.9414.9304.9184.9074.8954.883TE300.0K4.4904.4874.486D11.00000000secTD01========CHANNELf1========NUC11HP115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300121MHzWDWEM7.34ppm4.95ppmppmSSB0LB0.30HzGB0PC1.00109876543210ppmi-PrNCONIr4.133.870.132.101.871.956.066.00i-PrCOClFigureS23.1HNMRspectrumofcomplex26(600MHz,CDCl3,300K)200.67181.72167.05140.31138.13127.17126.60126.54124.8964.6752.5548.3823.3719.82CurrentDataParametersNAMEDHASIiPr-COEXPNO2i-PrPROCNO1NCOF2-AcquisitionParametersNDate_20200414IrTime8.03i-PrCOINSTRUMav600ClPROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS8888DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG18390.4DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8525000MHz200180160140120100806040200ppmWDWEMSSB0LB1.00HzGB0PC1.40FigureS24.13CNMRspectrumofcomplex26(600MHz,CDCl3,300K)S13

137.3367.3307.3277.3227.3187.3127.1827.1787.1737.1697.1645.3094.6554.4572.3811.9791.9591.9351.9131.8741.8581.8201.8141.7991.7931.7651.7431.7051.6981.6851.6771.5551.4411.4351.4251.4201.4041.3991.3931.3831.3771.3721.2621.2561.2501.2401.234CurrentDataParameters4.6554.457NAME350EXPNO1PROCNO1F2-AcquisitionParametersDate_20200128Time15.311.9591.9131.8741.8581.8201.8141.7991.7931.7431.7051.6981.6851.5551.4411.4201.3991.3771.2561.234INSTRUMav600PROBHD5mmPABBOBB-PULPROGzg30TD65536SOLVENTCDCl3NS16ppmppmDS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG3627.3307.3277.3227.3127.1827.1787.1737.1697.164DW40.400usecDE6.50usecTE300.0K1.81.61.4ppmD11.00000000secTD01========CHANNELf1========NUC11HP115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300122MHzWDWEMSSB0LB0.30HzGB0ppmppmPC1.00Cy109876543210ppmNCONIr4.003.970.551.894.300.684.364.751.752.762.204.752.73CyCOClFigureS25.1HNMRspectrumofcomplex27(600MHz,CDCl3,300K)200.81181.92167.18140.34138.21127.10126.51126.49124.8965.1460.8648.3834.1030.9126.0725.67CurrentDataParametersNAMEDHASICy-COEXPNO2CyPROCNO1NCOF2-AcquisitionParametersNDate_20200416IrTime8.52INSTRUMav600CyCOPROBHD5mmPABBOBB-ClPULPROGzgpg30TD143880SOLVENTCDCl3NS9800DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG18390.4DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524960MHz200180160140120100806040200ppmWDWEMSSB0LB1.00HzGB0PC1.40FigureS26.13CNMRspectrumofcomplex27(600MHz,CDCl3,300K)S14

14CurrentDataParametersNAME3667.2897.2847.2807.2757.1917.1857.1827.1765.3094.5234.5194.5163.7203.7173.7143.1192.0422.0392.0362.0262.0232.0201.7101.7081.7061.6941.6921.6901.554EXPNO1PROCNO1F2-AcquisitionParametersDate_20200217Time15.36INSTRUMav600PROBHD5mmPABBOBB-7.1917.1857.1827.1762.0422.0392.0362.0262.0232.0201.7101.7081.7061.6941.6921.690PULPROGzg30TD65536SOLVENTCDCl3NS16DS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG362DW40.400usecDE6.50usecTE300.0KD11.00000000secppmppm1.70ppmTD01========CHANNELf1========NUC11HP115.00usec7.2897.2847.2807.2754.5234.5194.5163.7203.7173.714PL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300128MHzWDWEMSSB0LB0.30HzGB0PC1.00ppmppmppmMeNCONIrMeCOCl109876543210ppm1.891.861.991.875.951.000.98FigureS27.1HNMRspectrumofcomplex28(600MHz,CDCl3,300K)198.32181.83166.78141.98127.66122.8770.0148.0646.7635.51CurrentDataParametersNAMEBCPSIMe-COMeEXPNO2NCOPROCNO1NIrF2-AcquisitionParametersMeDate_20200522COTime7.52ClINSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS9000DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG18390.4DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524959MHzWDWEM200180160140120100806040200ppmSSB0LB1.00HzGB0PC1.40FigureS28.13CNMRspectrumofcomplex28(600MHz,CDCl3,300K)S15

15CurrentDataParametersNAME3527.2457.2397.2367.2307.1477.1427.1387.1334.8364.8254.8144.8024.7914.7054.7024.6993.6523.6483.6462.0302.0272.0242.0142.0112.0081.7781.7751.7731.7611.7591.7571.5561.3541.3431.3051.2941.262EXPNO1PROCNO1F2-AcquisitionParametersDate_20200128Time15.44INSTRUMav6007.1477.1427.1387.1332.0302.0272.0242.0142.0112.008PROBHD5mmPABBOBB-1.7781.7751.7731.7611.7591.7571.3541.3431.3051.294PULPROGzg30TD65536SOLVENTCDCl3NS16DS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG362DW40.400usecDE6.50usecTE300.0K7.15ppmppmppmppmD11.00000000secTD01========CHANNELf1========NUC11H7.2457.2397.2367.2304.7054.7024.6994.8364.8254.8144.8024.7913.6523.6483.646P115.00usecPL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300123MHzWDWEMSSB0LB0.30HzGB0PC1.007.24ppmppmppmppmi-PrNCONIri-PrCOCl109876543210ppm1.911.832.061.992.021.001.046.006.28FigureS29.1HNMRspectrumofcomplex29(600MHz,CDCl3,300K)198.91181.90166.87142.98126.54124.4665.0052.5149.9348.8922.4720.55i-PrCurrentDataParametersNCONAMEBCPSIiPr-CONEXPNO2IrPROCNO1i-PrCOF2-AcquisitionParametersClDate_20200415Time7.47INSTRUMav600PROBHD5mmPABBOBB-PULPROGzgpg30TD143880SOLVENTCDCl3NS8888DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG16384DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524995MHz200180160140120100806040200ppmWDWEMSSB0LB1.00HzGB0PC1.40FigureS30.13CNMRspectrumofcomplex29(600MHz,CDCl3,300K)S16

16CurrentDataParametersNAME3537.2177.2117.2087.2037.1237.1187.1147.1094.6794.6764.6724.3784.3644.3584.3524.3383.6323.6293.6262.3701.9811.9781.9641.8871.7181.7021.5761.5701.5491.5231.5171.3791.3561.3501.3001.2891.2871.2661.1401.1341.1271.1181.1121.1060.8940.8830.871EXPNO1PROCNO1F2-AcquisitionParametersDate_20200128Time15.52INSTRUMav600PROBHD5mmPABBOBB-7.1237.1187.1147.1091.9811.9781.9641.5761.5701.5491.5231.5171.1401.1341.1271.1181.1121.106PULPROGzg30TD65536SOLVENTCDCl3NS16DS2SWH12376.237HzFIDRES0.188846HzAQ2.6476543secRG114DW40.400usecDE6.50usecTE300.0KD11.00000000secppm2.00ppm1.6ppm1.15ppmTD01========CHANNELf1========NUC11H7.2177.2117.2087.203P115.00usec4.6794.6764.6724.3784.3644.3584.3524.3383.6323.6293.6261.3001.2891.2871.266PL1-2.00dBSFO1599.9337048MHzF2-ProcessingparametersSI32768SF599.9300187MHzWDWEMSSB0LB0.30HzGB0PC1.007.22ppmppmppmppm1.3ppmCyNCONIrCyCOCl109876543210ppm2.001.950.232.192.152.220.513.244.522.283.816.247.422.4624.84FigureS31.1HNMRspectrumofcomplex30(600MHz,CDCl3,300K)199.00182.12167.03143.09126.47124.4865.7160.5250.0248.6033.2331.1726.0025.6325.54CurrentDataParametersNAMEBCPSICy-COEXPNO2PROCNO1CyF2-AcquisitionParametersNCODate_20200417NTime8.45IrINSTRUMav600CyPROBHD5mmPABBOBB-COPULPROGzgpg30ClTD143880SOLVENTCDCl3NS9600DS4SWH35971.223HzFIDRES0.250008HzAQ1.9999321secRG16384DW13.900usecDE6.50usecTE300.0KD12.00000000secD110.03000000secTD01========CHANNELf1========NUC113CP19.00usecPL15.00dBSFO1150.8676037MHz========CHANNELf2========CPDPRG[2waltz16NUC21HPCPD275.00usecPL2-2.00dBPL1211.98dBPL1311.98dBSFO2599.9323997MHzF2-ProcessingparametersSI32768SF150.8524982MHzWDWEM200180160140120100806040200ppmSSB0LB1.00HzGB0PC1.40FigureS32.13CNMRspectrumofcomplex30(600MHz,CDCl3,300K)S17

17MeNCON1989.1Ir2069.5MeCOCl2065.81986.4i-PrNCONIri-PrCOClCy2063.01982.8NCONIrCyCOClFigureS33.IRspectraofcomplex25,26,and27(inCH2Cl2,NaClcell)S18

18MeNCONIrMeCOCl2067.71987.4i-PrNCONIr2064.81986.7i-PrCOClCyNCONIrCyCOCl2063.41984.5FigureS34.IRspectraofcomplex28,29,and30(inCH2Cl2,NaClcell)S19

196.56.50.970.976.06.05.55.51.001.00PhPh5.0SPh5.0SPh1.01N2’1.01N2’0.970.964.54.5i-PrCyNNNNCyi-Pr4.04.0PhPhSSNN0.07ppm20.14ppm2PhPh6.56.50.29PC1.00GB0LB0.30HzSSB0WDWEMSF599.9300121MHzSI32768F2-ProcessingparametersSFO1599.9337048MHzPL1-2.00dBP115.00usecNUC11H========CHANNELf1========TD01D11.00000000secTE300.0KDE6.50usecDW40.400usecRG256AQ2.6476543secFIDRES0.188846HzSWH12376.237HzDS2NS16SOLVENTCDCl3TD65536PULPROGzg30PROBHD5mmPABBOBB-INSTRUMav600Time15.01Date_20200306F2-AcquisitionParametersPROCNO1EXPNO1NAME373CurrentDataParameters0.66PC1.00GB0LB0.30HzSSB0WDWEMSF599.9300122MHzSI32768F2-ProcessingparametersSFO1599.9337048MHzPL1-2.00dBP115.00usecNUC11H========CHANNELf1========TD01D11.00000000secTE300.0KDE6.50usecDW40.400usecRG181AQ2.6476543secFIDRES0.188846HzSWH12376.237HzDS2NS16SOLVENTCDCl3TD65536PULPROGzg30PROBHD5mmPABBOBB-INSTRUMav600Time16.38Date_20200402F2-AcquisitionParametersPROCNO1EXPNO1NAME380CurrentDataParameters0.300.961.636.06.05.55.51.001.00PhPh5.0SPh5.0SPhNN2’1.002’1.000.990.974.54.5i-PrCyNNNN4.04.0Cyi-PrPhPhSSNN220.61ppm1.34ppmPhPhFigureS35.1HNMRspectrumofcrudemixturesofallylicarylationproducts(600MHz,CDCl3,300K)PC1.00GB0LB0.30HzSSB0WDWEMSF599.9300126MHzSI32768F2-ProcessingparametersSFO1599.9337048MHzPL1-2.00dBP115.00usecNUC11H========CHANNELf1========TD01D11.00000000secTE300.0KDE6.50usecDW40.400usecRG228.1AQ2.6476543secFIDRES0.188846HzSWH12376.237HzDS2NS16SOLVENTCDCl3TD65536PULPROGzg30PROBHD5mmPABBOBB-INSTRUMav600Time16.09Date_20200310F2-AcquisitionParametersPROCNO1EXPNO1NAME375CurrentDataParametersPC1.00GB0LB0.30HzSSB0WDWEMSF599.9300123MHzSI32768F2-ProcessingparametersSFO1599.9337048MHzPL1-2.00dBP115.00usecNUC11H========CHANNELf1========TD01D11.00000000secTE300.0KDE6.50usecDW40.400usecRG362AQ2.6476543secFIDRES0.188846HzSWH12376.237HzDS2NS16SOLVENTCDCl3TD65536PULPROGzg30PROBHD5mmPABBOBB-INSTRUMav600Time14.44Date_20200309F2-AcquisitionParametersPROCNO1EXPNO1NAME374CurrentDataParametersS20

20TableS1.Crystallographicdataofcomplex13.AsinglecrystalforX-raydiffractionanalysiswasgrownbytheslowdiffusionofn-hexaneintoaCH2Cl2solution.AllmeasurementsweremadeonaRigakuR-AXISRAPIDdiffractometerusinggraphitemonochromatedCu-Kαradiation.chemicalformulaC9H12Ag0.5Cl0.5NVoltage,Current40kV,40mAM(g/mol)205.86T(K)93CrystalColor,Habitcolorless,plate2qmax136.2°crystalsize0.23X0.18X0.08mmNo.Observations(Allreflections)19476crystalsystemorthorhombicNo.Variables1713LatticeTypePrimitiveReflection/ParameterRatio15.86a(Å)a=12.5051(2)Residuals:R1(I>2.00s(I))0.0302b(Å)b=10.1404(2)Residuals:R(Allreflections)0.0312c(Å)c=13.9616(3)Residuals:wR2(Allreflections)0.0783a(deg)90GoodnessofFitIndicator1.118b(deg)90MaxShift/ErrorinFinalCycle0.001-3g(deg)90MaximumpeakinFinalDiff.Map1.21e/ÅV(Å3)1770.42(6)MinimumpeakinFinalDiff.Map-0.64e-/Å3SpaceGroupPnma(#62)StructureSolutionDirectMethodsZvalue8(SHELXTDcalc1.545g/cm3Version2014/5)F000840µ(CuKα)10.448mm-1CCDC2025127containsthesupplementarycrystallographicdataforthispaper.ThesedatacanbeobtainedfreeofchargefromTheCambridgeCrystallographicDataCentreviahttp://www.ccdc.cam.ac.uk/structures.S21

21TableS2.Crystallographicdataofcomplex14.AsinglecrystalforX-raydiffractionanalysiswasgrownbytheslowdiffusionofn-hexaneintoaCH2Cl2solution.AllmeasurementsweremadeonaRigakuR-AXISRAPIDdiffractometerusinggraphitemonochromatedCu-Kαradiation.chemicalformulaC24H32AgClN2O0.48Voltage,Current40kV,40mAM(g/mol)499.53T(K)93CrystalColor,Habitcolorless,block2qmax136.5°crystalsize0.15X0.13X0.10mmNo.Observations(Allreflections)25038crystalsystemmonoclinicNo.Variables4129LatticeTypePrimitiveReflection/ParameterRatio15.88a(Å)a=20.7104(7)Residuals:R1(I>2.00s(I))0.0658b(Å)b=12.1171(4)Residuals:R(Allreflections)0.0868c(Å)c=18.1740(6)Residuals:wR2(Allreflections)0.1605a(deg)90GoodnessofFitIndicator1.062b(deg)98.093(7)MaxShift/ErrorinFinalCycle0.001-3g(deg)90MaximumpeakinFinalDiff.Map1.32e/ÅV(Å3)4515.3(3)MinimumpeakinFinalDiff.Map-0.87e-/Å3SpaceGroupC2/c(#15)StructureSolutionDirectMethodsZvalue8(SHELXTDcalc1.470g/cm3Version2014/5)F0002063µ(CuKα)8.347mm-1CCDC2025128containsthesupplementarycrystallographicdataforthispaper.ThesedatacanbeobtainedfreeofchargefromTheCambridgeCrystallographicDataCentreviahttp://www.ccdc.cam.ac.uk/structures.S22

22TableS3.Crystallographicdataofcomplex20.AsinglecrystalforX-raydiffractionanalysiswasgrownbytheslowdiffusionofn-hexaneintoaCH2Cl2solution.AllmeasurementsweremadeonaRigakuR-AXISRAPIDdiffractometerusinggraphitemonochromatedCu-Kαradiation.chemicalformulaC31H38IrClN2Voltage,Current40kV,40mAM(g/mol)666.28T(K)93CrystalColor,Habityellow,plate2qmax136.4°crystalsize0.18X0.17X0.08mmNo.Observations(Allreflections)29843crystalsystemmonoclinicNo.Variables4829LatticeTypePrimitiveReflection/ParameterRatio15.09a(Å)a=9.3978(2)Residuals:R1(I>2.00s(I))0.0281b(Å)b=17.2576(3)Residuals:R(Allreflections)0.0324c(Å)c=16.6526(3)Residuals:wR2(Allreflections)0.0757a(deg)90GoodnessofFitIndicator1.074b(deg)102.190(7)MaxShift/ErrorinFinalCycle0.001-3g(deg)90MaximumpeakinFinalDiff.Map1.26e/ÅV(Å3)2639.88(11)MinimumpeakinFinalDiff.Map-1.18e-/Å3SpaceGroupP21/c(#14)StructureSolutionDirectMethodsZvalue4(SHELXTDcalc1.676g/cm3Version2014/5)F0001328µ(CuKα)10.879mm-1CCDC2025129containsthesupplementarycrystallographicdataforthispaper.ThesedatacanbeobtainedfreeofchargefromTheCambridgeCrystallographicDataCentreviahttp://www.ccdc.cam.ac.uk/structures.S23

23TableS4.Crystallographicdataofcomplex23.AsinglecrystalforX-raydiffractionanalysiswasgrownbytheslowdiffusionofn-hexaneintoaCH2Cl2solution.AllmeasurementsweremadeonaRigakuR-AXISRAPIDdiffractometerusinggraphitemonochromatedCu-Kαradiation.chemicalformulaC13H18Ir0.5Cl0.5NVoltage,Current40kV,40mAM(g/mol)302.11T(K)93CrystalColor,Habityellow,plate2qmax136.3°crystalsize0.13X0.12X0.06mmNo.Observations(Allreflections)25946crystalsystemorthorhombicNo.Variables2279LatticeTypePrimitiveReflection/ParameterRatio15.83a(Å)a=10.9536(2)Residuals:R1(I>2.00s(I))0.0229b(Å)b=15.8195(3)Residuals:R(Allreflections)0.0251c(Å)c=13.7274(3)Residuals:wR2(Allreflections)0.0509a(deg)90GoodnessofFitIndicator1.137b(deg)90MaxShift/ErrorinFinalCycle0.002-3g(deg)90MaximumpeakinFinalDiff.Map0.78e/ÅV(Å3)2378.69(8)MinimumpeakinFinalDiff.Map-1.48e-/Å3SpaceGroupPbcm(#57)StructureSolutionDirectMethodsZvalue8(SHELXTDcalc1.687g/cm3Version2014/5)F0001200µ(CuKα)11.998mm-1CCDC2025130containsthesupplementarycrystallographicdataforthispaper.ThesedatacanbeobtainedfreeofchargefromTheCambridgeCrystallographicDataCentreviahttp://www.ccdc.cam.ac.uk/structures.S24

241StructuralAnalysesofNHCligandswithuseofSambVca2.1programStructuralanalysesofNHCswithbicyclicstructures(DHASIMe,DHASIiPr,DHASICy,BCPSIMe,BCPSIiPr,BCPSICy),IMe,IiPr,andICywereperformedusingparametersshownbelow.OtherligandsthanNHCsandsolventmoleculeswereexcludedfromthecalculations.[(DHASIMe)AgCl]2,[(DHASIiPr)NiCpCl]3,[(DHASIiPr)CuCl]3,[(DHASICy)NiCpCl]5,[(BCPSIMe)AgCl]6,[(BCPSIiPr)AgCl]13,[(BCPSICy)AgCl]14,[(IMe)AuCl]7,[(IiPr)AuCl]8,[(ICy)AuCl]8complexeswereusedforthecalculations.Parametersforthecalculations•NHC–Metalbonddistance···························2.00Å•Bondiradiiscaledby1.17•Meshspacingfornumericalintegration············0.10(a)(b)(c)MeNNAgClMe%VBur27.6%VBur27.1(d)(e)%VBur26.2%VBur24.8FigureS36.(a)Structureofthe[(DHASIMe)AgCl]complex.2Stericmapsand%VBurforDHASIMecalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).S25

25(a)(b)(c)NNNiCl%VBur29.2%VBur29.1(d)(e)%VBur29.2%VBur29.0FigureS37.(a)Structureofthe[(DHASIiPr)NiCpCl]complex.3Stericmapsand%VBurforDHASIiPrcalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).(a)(b)(c)NNCuCl%VBur34.1%VBur33.9(d)(e)%VBur33.5%VBur32.3FigureS38.(a)Structureofthe[(DHASIiPr)CuCl]complex.4Stericmapsand%VBurforDHASIiPrcalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).S26

26(a)(b)(c)i-PrNNIri-PrCl%VBur28.9%VBur29.1(d)(e)%VBur29.4%VBur29.3FigureS39.(a)Structureofthe[Ir(COD)Cl(DHASIiPr)]complex20.Stericmapsand%VBurforDHASIiPrcalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).(a)(b)(c)NNNiCl%VBur30.3%VBur31.3(d)(e)%VBur32.3%VBur32.9FigureS40.(a)Structureofthe[(DHASICy)NiCpCl]complex.5Stericmapsand%VBurforDHASICycalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).S27

27(a)(b)(c)MeNNAgClMe%VBur29.8%VBur29.5(d)(e)%VBur28.6%VBur27.0FigureS41.(a)Structureofthe[(BCPSIMe)AgCl]complex.6Stericmapsand%VBurforBCPSIMecalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).(a)(b)(c)NNAgCl%VBur39.0%VBur38.8(d)(e)%VBur38.0%VBur35.9FigureS42.(a)Structureofthe[(BCPSIiPr)AgCl]complex13.Stericmapsand%VBurforBCPSIiPrcalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).S28

28(a)(b)(c)i-PrNNIri-PrCl%VBur29.2%VBur29.6(d)(e)%VBur30.0%VBur29.9FigureS43.(a)Structureofthe[Ir(COD)Cl(BCPSIiPr)]complex23.Stericmapsand%VBurforDHASICycalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).(a)(b)(c)NNAgCl%VBur32.9%VBur34.0(d)(e)%VBur35.0%VBur35.2FigureS44.(a)Structureofthe[(BCPSICy)AgCl]complex14.Stericmapsand%VBurforBCPSIMecalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).S29

29(a)(b)(c)NNMeMeAuCl%VBur26.4%VBur24.2(d)(e)%VBur21.9%VBur19.3FigureS45.(a)Structureofthe[(IMe)AuCl]complex(CCDC#264465).7Stericmapsand%VBurforIMecalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).(a)(b)(c)NNAuCl%VBur27.6%VBur26.7(d)(e)%VBur25.8%VBur24.7FigureS46.(a)Structureofthe[(IiPr)AuCl]complex(CCDC#250395).8Stericmapsand%ViBurforIPrcalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).S30

30(a)(b)(c)NNAuCl%VBur27.7%VBur26.9(d)(e)%VBur26.6%VBur26.2FigureS47.(a)Structureofthe[(ICy)AuCl]complex(CCDC#250396).8Stericmapsand%VBurforICycalculatedwithasphereradiusof3.5,4.0,4.5,5.0Å,respectively(b–e).Oneoftwomoleculesintheasymmetricunitwasusedforthecalculation.TableS5.%VBurforNHCswithorwithoutbicyclicarchitectures.R(Å)2[(BCPSIMe)AgCl]6[(BCPSIiPr)AgCl][(BCPSICy)AgCl][(DHASIiPr)NiCpCl]3[(DHASICy)NiCpCl]5[(DHASIMe)AgCl]3.527.629.839.032.929.230.34.027.129.538.834.029.131.34.526.228.638.035.029.232.35.024.827.035.935.229.032.9R(Å)4[(IMe)AuCl]7[(IiPr)AuCl]8[(ICy)AuCl]8[Ir(COD)Cl(BCPSIiPr)][Ir(COD)Cl(DHASIiPr)][(DHASIiPr)CuCl]3.529.228.934.126.427.627.74.029.629.133.924.226.726.94.530.029.433.521.925.826.65.029.929.332.319.324.726.2S31

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