Thermal and Photochemical Silicon−Carbon Bond Activation in Donor-Stabilized Platinum(0)−Alkyne Complexes

Autor: Muller, C., Lachicotte, R. J., Jones, W. D.
Zdroj: Organometallics; March 2002, Vol. 21 Issue: 6 p1190-1196, 7p
Abstrakt: Reaction of Pt(COD)2 with Me3SiC&tbd1;CPh and a bidentate chelating ligand leads to the formation of the corresponding donor-stabilized Pt-η2-alkyne complexes (PN)Pt(η2-Me3SiC&tbd1;CPh) (1) and (dcpe)Pt(η2-Me3SiC&tbd1;CPh) (3) (PN = (diisopropylphosphinodimethylamino)ethane; dcpe = bis(dicyclohexylphosphino)ethane). The nitrogen donor ligand in 1 facilitates the cleavage of the Si−C(sp) bond, and the Pt(II) complex (PN)Pt(SiMe3)(C&tbd1;CPh) (2) is formed at room temperature. In contrast, the bisphosphino-substituted compound 3 has been isolated as a thermally robust Pt(0) complex. However, the silicon−carbon bond in the latter compound can be photochemically activated, and the oxidative addition product (dcpe)Pt(SiMe3)(C&tbd1;CPh) (4) is generated. Both Si−C(sp) bonds in Me3Si−C&tbd1;C−C&tbd1;C−SiMe3 have been thermally activated by a (PN)Pt fragment to afford the dinuclear Pt(II) species (PN)Pt(SiMe3)−C&tbd1;C−C&tbd1;C−Pt(SiMe3)(PN) (6).
Databáze: Supplemental Index