The complexes cis-PtCl(Et)(diphosphine) [diphosphine = 1,3-bis(diphenylphosphino)propane, 1,4- bis(diphenylphosphino)butane] were used as model compds. for the hydroformylation of olefin catalyzed by PtCl2/diphosphine/SnCl2. Reaction with SnCl2 gives cis-Pt(SnCl3)(C2H5)(diphosphine), which in the absence of free ethylene decomp. to form the species cis-PtCl2(diphosphine) via an unstable hydrido species. Both the chloro- and trichlorostannate-alkyl complexes react with CO to give the acyl species cis-PtX(COEt)(diphosphine) (X = Cl or SnCl3). When the diphosphine is 1,4-bis(diphenylphosphino)butane, oligomeric acyl complexes of trans geometry are formed. Preliminary studies of the reactivity of the acyl complexes with mol. hydrogen show that only the complexes bearing the Pt-SnCl3 moiety react at ambient conditions giving propanal as the only obsd. org. product.
On the mechanism of platinum(II)/tin(II) chloride catalyzed hydroformylation of olefins. Studies of the reactivity ofalkyl complexes containing chelating diphosphines
TONIOLO, Luigi;
1988-01-01
Abstract
The complexes cis-PtCl(Et)(diphosphine) [diphosphine = 1,3-bis(diphenylphosphino)propane, 1,4- bis(diphenylphosphino)butane] were used as model compds. for the hydroformylation of olefin catalyzed by PtCl2/diphosphine/SnCl2. Reaction with SnCl2 gives cis-Pt(SnCl3)(C2H5)(diphosphine), which in the absence of free ethylene decomp. to form the species cis-PtCl2(diphosphine) via an unstable hydrido species. Both the chloro- and trichlorostannate-alkyl complexes react with CO to give the acyl species cis-PtX(COEt)(diphosphine) (X = Cl or SnCl3). When the diphosphine is 1,4-bis(diphenylphosphino)butane, oligomeric acyl complexes of trans geometry are formed. Preliminary studies of the reactivity of the acyl complexes with mol. hydrogen show that only the complexes bearing the Pt-SnCl3 moiety react at ambient conditions giving propanal as the only obsd. org. product.
I documenti in ARCA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
