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Revealing the P-B coupling event in the rhodium catalysed dehydrocoupling of phosphine-boranes H3B center dot PR2H (R = Bu-t, Ph)
Authors
MA Huertos
AS Weller
Publication date
1 January 2013
Publisher
'Royal Society of Chemistry (RSC)'
Doi
Cite
Abstract
We demonstrate that [Rh(η6-FC6H5)(Ph2PCH2CH2CH2PPh2 )][BArF4] is a competent catalyst for the dehydrocoupling of H3B·PR2H to give H3B·PR2BH2·PR2H (R = Ph, tBu). The isolation of intermediates (R = tBu, Ph) and kinetic/isotopic labelling experiments (for R = Ph) point to a mechanism, for R = Ph, in which the rate-limiting process for dehydrocoupling involves B-H activation, while the turnover limiting process for catalysis involves the substitution of the oligomeric product at the metal, which forms a strong chelate complex with a Rh(iii) centre, by H3B·PPh2H. When R = tBu no chelate product complex forms, and it is speculated that the dehydrocoupling process now becomes turnover limiting. These observations provide, for the first time we believe, data on the P-B bond forming events that are central to the dehydrocoupling and dehydropolymerisation of phosphine-boranes. This journal is © The Royal Society of Chemistry 2013
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Last time updated on 30/09/2015
Oxford University Research Archive (ORA)
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Last time updated on 18/04/2020