Reactivity of silyl-substituted heterobimetallic iron–platinum hydride complexes: Part III. Alkyne insertions into the platinum–hydride bond and competition between μ-vinylidene and dimetallacyclopentenone formation

Abstract: Insertion of aliphatic 1-alkynes such as tert-butylacetylene, 1-hexyne or 1,6-heptadiyne into the Pt–H bond of the heterobimetallic hydride complex [(OC)3Fe{Si(OMe)3}(μ-dppm)Pt(H)(PPh3)] (1) (dppm=Ph2PCH2PPh2) leads to the formation of an isomeric mixture of μ-vinylidene complexes [(OC)3Fe{μ-Cx3bc;-dppm)Pt(PPh3)] (2a: R= tert-Bu, 2b: R= n-Bu, 2c: R=(CH2)3–Cimetallacyclopentenones [(OC)2Fe{μ-C(=O)CRc;-dppm)Pt(PPh3)] (3a: R= tert-Bu, 3b: R= n-Bu, 3c: R=(CH2)3–Cmolecular structures of 2a and 3c have been determined by single-crystal X-ray diffraction. [Copyright &y& Elsevier]