Aromatic and aldehyde carbon–hydrogen bond activation at cationic Rh(III) centers. Evaluation of electronic substituent effects on aldehyde binding and C–H oxidative addition
作者： Britton K. Corkey , Felicia L. Taw , Robert G. Bergman , Maurice Brookhart
DOI: 10.1016/J.POLY.2004.09.005
关键词: Carbon–hydrogen bond activation 、 Oxidative addition 、 Chemistry 、 Rhodium 、 Adduct 、 Nuclear magnetic resonance spectroscopy 、 Stereochemistry 、 Decarbonylation 、 Aldehyde 、 Aryl
摘要: Cationic rhodium methyl complexes, [Cp*(PMe 3 )Rh(Me)(CH 2 Cl )]BAr' 4 (1) and [Cp*(P(OMe) (3), react with benzene to yield the corresponding phenyl )Rh(Ph)(CH (6) (7). First-order rate constants observed in 1.1 M CD at 25 °C are (2.1 ′ 0.2) × 10 - 5 s 1 (1.9 , respectively. Reactions of p-X-substituted benzaldehydes (X = -CF -CH -OMe) initially produce σ-aldehyde adducts, [Cp*(L)Rh(Me)(p-XC 6 H CHO)]BAr' (L PMe (15), P(OMe) (16)). Exchange free bound aldehyde occurs via a dissociative process quantitative NMR measurements show that complexes exchange faster than those less basic aldehydes more (p-CF C CHO > p-CH (C CHO). The adducts undergo C-H bond activation methane plus acyl [Cp*(L)Rh(C(O)C X)(p XC (17), (18)). Rates correlated rates; barriers weakly lower strongly aldehydes. In case L decarbonylation cleanly form aryl carbonyl )Rh(C X)(CO)]BAr' . For is complicated process; some intermediates products have been identified by spectroscopy.
osti.gov
elsevier.com
sci-hub.se 参考文章(33)
Peter Burger, Robert G. Bergman, Facile intermolecular activation of carbon-hydrogen bonds in methane and other hydrocarbons and silicon-hydrogen bonds in silanes with the iridium(III) complex Cp*(PMe3)Ir(CH3)(OTf) Journal of the American Chemical Society. ,vol. 115, pp. 10462- 10463 ,(1993) , 10.1021/JA00075A113
Alan Fersht, Enzyme structure and mechanism ,(1977)
David M. Tellers, Cathleen M. Yung, Bruce A. Arndtsen, Dan R. Adamson, Robert G. Bergman, Electronic and Medium Effects on the Rate of Arene C−H Bond Activation by Cationic Ir(III) Complexes Journal of the American Chemical Society. ,vol. 124, pp. 1400- 1410 ,(2002) , 10.1021/JA011809U
A.E. Shilov, A.A. Shteinman, Activation of saturated hydrocarbons by metal complexes in solution Coordination Chemistry Reviews. ,vol. 24, pp. 97- 143 ,(1977) , 10.1016/S0010-8545(00)80336-7
ULRICH FEKL, KAREN I. GOLDBERG, HOMOGENEOUS HYDROCARBON CH BOND ACTIVATION AND FUNCTIONALIZATION WITH PLATINUM Advances in Inorganic Chemistry. ,vol. 54, pp. 259- 320 ,(2003) , 10.1016/S0898-8838(03)54005-3
Peter J. Alaimo, Bruce A. Arndtsen, Robert G. Bergman, Synthesis of Tertiary and Other Sterically Demanding Alkyl and Aryl Complexes of Iridium by Aldehyde C−H Bond Activation Journal of the American Chemical Society. ,vol. 119, pp. 5269- 5270 ,(1997) , 10.1021/JA970245K
Robert H. Crabtree, Charles P. Parnell, Arene and cyclohexadienyl complexes as intermediates in the selective catalytic dehydrogenation of cyclohexenes to arenes Organometallics. ,vol. 4, pp. 519- 523 ,(1985) , 10.1021/OM00122A015
Amy B. Pangborn, Michael A. Giardello, Robert H. Grubbs, Robert K. Rosen, Francis J. Timmers, Safe and Convenient Procedure for Solvent Purification Organometallics. ,vol. 15, pp. 1518- 1520 ,(1996) , 10.1021/OM9503712
Mark J. Burk, Robert H. Crabtree, Selective catalytic dehydrogenation of alkanes to alkenes Journal of the American Chemical Society. ,vol. 109, pp. 8025- 8032 ,(1987) , 10.1021/JA00260A013
Robert H. Crabtree, Jean M. Mihelcic, Jennifer M. Quirk, Iridium complexes in alkane dehydrogenation Journal of the American Chemical Society. ,vol. 101, pp. 7738- 7740 ,(1979) , 10.1021/JA00520A030