A Room Temperature Direct Metal Insertion into a Nonstrained Carbon−Carbon Bond in Solution. C−C vs C−H Bond Activation

Abstract

The diphosphine 1,3-bis[(di-tert-butylphosphino)methyl]-2,4,6-trimethylbenzene (1a) upon reacting with the rhodium and iridium olefin complexes M2(olefin)4Cl2 (M = Rh, Ir) undergoes rapid, selective metal insertion into the strong unstrained aryl−methyl bond under very mild conditions (room temperature), yielding ClM(CH3)[C6H(CH3)2(CH2P(t-Bu)2)2] (M = Rh (4a), Ir (7a)). The carbon−carbon bond activation is competitive with a parallel C−H activation process, which results in formation of complexes ClMH(L)[CH2C6H(CH3)2(CH2P(t-Bu)2)2] (M = Rh (3a), Ir (6a); L = cyclooctene in the case of 6a and is absent in 3a). Complexes 3a and 6a undergo facile C−H reductive elimination (at room temperature (3a) or upon moderate heating (6a)), followed by C−C oxidative addition, resulting in clean formation of 4a and 7a, respectively. The C−C bond activation products are stable under the reaction conditions, demonstrating that this process is the thermodynamically favorable one. X-ray single-crystal analysis of 4a demonstrates that the rhodium atom is located in the center of a square pyramid, with the methyl group occupying the position trans to the vacant coordination site. Direct kinetic comparison of the C−C and C−H activation processes shows thatin contrast to theoretical calculationsmetal insertion into the carbon−carbon bond in this system is not only thermodynamically but also kinetically preferred over the competing insertion into the carbon−hydrogen bond. When the ligand 1,3-bis[(di-tert-butylphosphino)methyl]-2,4,6-trimethyl-5-methoxybenzene (1b), bearing the strong electron-donating methoxy group in the position trans to the Ar−CH3 bond to be cleaved, was used instead of 1a, no effect on the reaction rate or on the ratio between the C−H and C−C activation products was observed. Our observations indicate that the C−C oxidative addition proceeds via a three-centered mechanism involving a nonpolar transition state, similar to the one proposed for C−H activation of hydrocarbons. An η2-arene complex is not involved in the C−C activation process.