Abstract
Efficient alkyne hydrosilylation mediated by well-defined platinum(ii) bis(ethoxycarbene) complexes of the Fischer-type prepared by facile transmetallation.
Highlights
Acyclic heteroatom-stabilized carbene complexes of platinum(II) have been known since 1915,1–3 and yet the number of isolated examples are limited
PtII Fischer carbene complexes with thiophene substituents, are synthesized for the first time employing the methodology of carbene transfer, and their use as catalysts for the alkyne hydrosilylation reaction is investigated
Synthesis of platinum(II) Fischer carbene complexes (FCCs) PtII multicarbene complexes were synthesized by transmetallation reactions of the chromium or tungsten carbonyl FCC precursors P1–P4, containing either a 2-thienyl (T) or a 5-thieno[2,3-b]thienylene (TT) substituent, via a modified procedure of that reported by Sierra and co-workers (Scheme 1).[7]
Summary
Acyclic heteroatom-stabilized carbene complexes of platinum(II) have been known since 1915,1–3 and yet the number of isolated examples are limited. The cis-biscarbene complexes of 3 and 4 have three isomeric possibilities where the TT spacers and amino fragments have various orientations to yield different geometric stereoisomers (Fig. 2) due to restricted rotation enforced by the sterically demanding thieno[2,3-b]thienylene carbene substituent and the amino group with increased Ccarbene–N bond order.
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