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- W2184462054 abstract "Intermolecular equilibrium isotope effects (EIEs) were measured (26.5 °C) and calculated for (silox)2- ( t Bu3SiND)TiRD (1-ND-RD) + RHH a (silox)2( t Bu3SiNH)TiRH (1-RH) + RDD: RHH/RDD ) CH4/CD4, 2.00(6), calcd 1.88; C2H6/C2D6, 2.22(8), 1.93; c C3H6/ c C3D6, 1.71(4), 1.48; C2H4/C2D4, 1.41(11), 1.34; C6H6/ C6D6, 1.22(7), 1.26; C7H8/C7D8 (50.0 °C), 1.59(6), 1.55. Related intramolecular EIEs for (silox) 2( t Bu3SiND)- TiR' (1-ND-R') a (silox)2( t Bu3SiNH)TiR (1-R) are provided: RH ) RD ) CH3D, 3.16(25), calcd 2.60; CH2D2, 1.13(8), 0.911; CHD3, 0.389(20), 0.303; CH3CD3, 1.53(3), 1.44; 1,1- c C3H4D2, 2.58(6), 2.53; trans- HDCdCHD, 1.00(2), 1.00; 1,3,5-C6H3D3, 1.273(4), 1.25; PhCH2D (50.0 °C), 2.06(2), 1.98. Calculations of pertinent model complexes (e.g., (HO)2(H2N)TiR (1'-R)) generated the vibrational frequencies necessary to interpret the EIEs in terms of a statistical mechanics description utilizing gas-phase partition functions; EIE ) SYM MMI EXC EXP(-(¢¢ZPE/kBT)). The large MMI term in the intermolecular casessa consequence of using perprotio vs perdeuterio small molecule substratessis attenuated by EXC and EXP(-(¢¢ZPE/kBT)) contributions derived from low-energy core vibrations. The EIEs are differentiated on the basis of the EXP (-(¢¢ZPE/kBT)) term, with CH-based bending vibrations playing the major role. Substrate bending vibrations that are absent in intramolecular cases are primarily responsible for the greater intermolecular values. Using measured (or calculated) EIEs and kinetic isotope effects for 1,2-RH-elimination (KIE elim) from 1-R, KIEaddn values for 1,2-RH-addition to putative intermediate (silox) 2TidNSi t Bu3 (2) were inferred via EIE ) KIEaddn/ KIEelim. Extraordinary intermolecular KIEaddn values ranging from 30 (CH4/CD4 ,C 2H6/C2D6 )t o 9( C 6H6/ C6D6) are consistent with previous mechanistic accounts and may be conventionally rationalized." @default.
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- W2184462054 date "2000-01-01" @default.
- W2184462054 modified "2023-09-27" @default.
- W2184462054 title "Inferred Kinetic Isotope Effects for RH/D Addition to Transient (silox)2TidNSi t Bu3" @default.
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