Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 607, Issue 1-2, Pages 164-174Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/S0022-328X(00)00333-8
Keywords
platinum; nickel; acyl-complex; CO insertion; DFT calculation; metallacycle
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Reactions of CO with nickel or platinum complexes of cyclic alkynes or arynes form initially metallacyclobutenone species, which undergo further insertion of CO to give five-membered metallacycles. The differences in regioselectivity observed for nickel or platinum have been investigated computationally by DFT methods. Although both metals prefer insertion of the second CO via a five-coordinate mechanism, the formation of the five-membered nickelacycle is under thermodynamic control, leading to a symmetrical nickelacyclopentene-2,4-dione complex, whereas platinum yields the kinetically favoured platinacyclopentene-2,3-dione complex. (C) 2000 Elsevier Science S.A. All rights reserved.
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