Chemistry of metal hydrides. III. Preparation of trans-[PtCl(CO)(R3P)2]+ cations and related compounds

Abstract

The cations Zrans-[PtCl(CO)L2]+, where L = triethylor triphenylphosphine, have been synthesized according to the reactions:These platinum(II) cations are isoelectronic with [IrCl(CO)(Ph3P)2] and its rhodium(I) analog but are much less reactive, although the carbonyl group is readily displaced by Cl-. These syntheses allow reinterpretation of previous results1 on the reaction of frim-[PtHCl(Et3P)2] with C2F4 in the presence of Pyrex glass. The Zra«s-[PtCl(CO)(Et3P)2]+ cation is formed during this reaction, the counteranions being BF4-and the previously unknown SiF5ion, in this case stabilized products was not achieved.

Chemistry of metal hydrides. VI. Cationic platinum(II) carbonyls stabilized with tertiary arsines and stibines

“…The synthesis of dihalo-bridged diplatinum cations by reaction of the appropriate dihalobisarsine (or stibine) complex with boron trifluoride as previously reported (2), was successful for [Pt2Cl2(R3M),:I[BF4], where M = As or Sb, and R = ethyl. For R = phenyl, a sequence involving silver tetrafluoroborate at room temperature was employed (4).…”

“…These new dimeric cations, like their phosphine analogues, react in minutes in a chloroform suspension with carbon monoxide at 1 atm pressure, to yield a series of well defined carbony1 platinum(I1) salts in the trans configuration (2 For personal use only. M = P or As are in marked contrast to the low-melting, yellow-orange stibine salt (Table I).…”

“…, and the alkoxy carbonyls [PtX(COOR)(Ph,P),] have recently been studied (1,2). Analogous arsine and stibine complexes have now been prepared, and compared to the former both in physical properties and chemical reactivity.…”

“…An examination of the [PtC1(CO)(R3P),lf cation (2) has been prompted by the well-known catalytic activity of the isoelectronic species [RhCl(Ph,P),] and trans-[IrC1(CO)(Ph3P),] in the homogeneous hydrogenation of olefins (3). Phosphine-stabilized platinum(I1) .…”

Chemistry of metal hydrides. VII. An iridium(III) carbonyl cation and the formation of iridium(III) hydridocarbonyls

“…In previous papers (1)(2)(3), reactions leading to the insertion of unsaturated reactants in the Pt-H bond of Pt(I1) 4-coordinate hydrides were described, as well as interconversion reactions (4) between such hydrides and cationic platinum(I1) carbonyl salts. While the effects of different ligands on such reactions require further study ( 5 ) , it is also clear that the square planar geometry of these hydrides may be a significant factor.…”