Catalytic Homologation of Vinyltributylstannane to Allyltributylstannane by Mo(IV) Complexes in the Presence of Ethylene
- 29 January 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (7) , 1948-1949
- https://doi.org/10.1021/ja039173p
Abstract
We have found that CH2CHSnBu3 is converted into CH2CHCH2SnBu3 catalytically in the presence of Mo(IV) olefin complexes such as Mo(NAr)(CH2CH2)[biphen] (where Ar = 2,6-i-Pr2C6H3 and [biphen]2- = 3,3‘-di-tert-butyl-5,5‘,6,6‘-tetramethyl-1,1‘-biphenyl-2,2‘-diolate). The proposed mechanism involves formation of a metalacyclopentane (MC4) complex from ethylene and CH2CHSnBu3, “contraction” of this MC4 complex to a metalacyclobutane (MC3) complex, and finally metathesis of the MC3 complex to give CH2CHCH2SnBu3 and Mo(NAr)(CH2)[biphen]. These new findings suggest (inter alia) that contraction of an MC4 ring to an MC3 ring may be a much more common mode of decomposition of metalacyclopentane rings in d0 complexes than previously believed.Keywords
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