Yuzhong Chen, WaiChung Chan, C. Lau
Mar 18, 1997
Citations
0
Influential Citations
50
Citations
Journal
Organometallics
Abstract
Treatment of TpRuCl(PPh3)(CH3CN) (Tp = hydrotris(pyrazolyl)borate) with NaBH4 in ethanol did not yield the expected hydride complex TpRuH(PPh3)(CH3CN) (2) but rather the methyl carbonyl complex TpRu(CH3)(CO)(PPh3) (1b). Formation of 1b was due to decarbonylation of ethanol by 2 generated in situ by NaBH4 reduction of TpRuCl(PPh3)(CH3CN). Analogous reactions in the presence of other primary alcohols RCH2OH (R = H, C2H5, n-C3H7, C6H5, C6H4CH3-4, and C6H4Cl-4) led to the corresponding σ-organyl complexes TpRuR(CO)(PPh3). A common feature of the reactions is that the R groups of alcohols RCH2OH become the σ-organyl groups in the final metal complexes. A mechanism involving metal−η2-aldehyde and −η2-dihydrogen intermediates is proposed for the decarbonylation reaction. This is supported by the observation of the η2-dihydrogen complex TpRuH(H2)(PPh3) (3) during the decarbonylation reaction. 3 was synthesized independently by heating a THF solution of 2 under 40 atm of H2 at 60 °C for 48 h or by heating 2 in CH3...