Issue 4, 1979

Reactions of electroneutral alkoxy(organo)carbene complexes of platinum(II)

Abstract

The carbene complexes cis-[PtCl2(PR3){C(OR′)(CH2R″)}](1; R3= Me2Ph or Et3; R′= Me, Et, or Prn; R″= Me, Et, or Ph) react rapidly with CD3OD to yield cis-[PtCl2(PR3){C(OR′)(CD2R″)}], then slowly by alkoxy-group exchange to cis-[PtCl2(PR3){C(OCD3)(CD2R″)}]. Dimethylamine reacts by proton abstraction to form [PtCl(PR3)(NMe2H){C(OR′)[double bond, length half m-dash]CHR″}]. The carbene complexes react with chloride ions by R′Cl elimination to form the acyls [Pt2(µ-Cl)2(PR3)2(COCH2R″)2]. Thermolyses of (1) produce the same products. These reactions are compared with those of related cationic carbene complexes. Treatment of (1) by PR3 in the presence of Ag-[S(CF3)O3] leads to the cationic carbene complex trans-[PtCl(PR3)2{C(OR′)(CH2R″)}][S(CF3)O3] which can also be made by the action of R′SO3CF3 on trans-[PtCl(PR3)2(COCH2R″)]. Halogen abstraction from (1) by Ag[S(CF3)O3], MeSO3CF3, or EtSO3CF3 produces binuclear halide-bridged cationic complexes [Pt2(µ-Cl)2(PR3)2{C(OR′)(CH2R″)}2][S(CF3)O3]2. These are extremely powerful alkylating agents, and alkylate the [S(CF3)O3] anions in solution.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1979, 690-694

Reactions of electroneutral alkoxy(organo)carbene complexes of platinum(II)

G. K. Anderson and R. J. Cross, J. Chem. Soc., Dalton Trans., 1979, 690 DOI: 10.1039/DT9790000690

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