182009-46-7Relevant academic research and scientific papers
Reactions of cis- and trans-silyl(methyl)platinum(II) complexes with phenylacetylene. Remarkable effect of cis and trans configurations on the reactivity
Ozawa, Fumiyuki,Hikida, Toshihiko
, p. 4501 - 4508 (2008/10/08)
Two geometrical isomers of silyl(methyl)platinum complexes cis- and trans-PtMe(SiPh3)L2 (L = PMe2Ph, PMePh2) exhibited entirely different reactivities toward phenylacetylene. Reactions of cis-PtMe(SiPh3)L2 (L = PMe2Ph (1a), PMePh2 (1b)) with phenylacetylene readily proceeded at room temperature in benzene to give the acetylene-insertion products cis-PtMe-{C(Ph)=CH(SiPh3)}L2 (L = PMe2Ph (3a), PMePh2 (3b), respectively). In contrast, trans-PtMe(SiPh3)L2 complexes (L = PMe2Ph (2a), PMePh2 (2b)) were totally inactive toward acetylene insertion. The cis-organo(silyl)platinum complexes cis-PtMe(SiPh3)(PMe3)(PMePh2) (1c) and cis-Pt(COEt)(SiPh3)(PMe2Ph)2 (6d) also underwent the insertion of phenylacetylene into the Pt-SiPh3 bond to provide quantitative yields of cis-PtMe{C(Ph)=CH(SiPh3)}(PMe3)-(PMePh2) (3c) and cis-Pt(COEt){C(Ph)=CH(SiPh3)}(PMe2Ph)2 (7), respectively. The molecular structures of 3a,c were determined by X-ray diffraction studies. Kinetic studies on the formation of 7 revealed the insertion process initiated by rate-determining displacement of one of the PMe2Ph ligands in 6d with phenylacetylene.
