(Phosphido)platinum Complexes by Sodium-Promoted Reaction ofcis-PtCl2(PHCy2)2 − Synthesis and Crystal Structure of [trans-Pt(PCy2H)2(PCy2)Cl], a Rare Example of a Terminal (Phosphido)platinum(II) Complex

Abstract

cis‐PtCl2(PHCy2)2 (1) reacts at 0 °C in toluene with sodium metal to give the dinuclear PtI complexes cis‐[(PHCy2)(H)Pt(μ‐PCy2)]2 (2) and [(PHCy2)(Cl)Pt(μ‐PCy2)Pt(PHCy2)2](Pt−Pt) (3). On standing in solution, complex 3 isomerizes to trans‐[(PHCy2)(Cl)Pt(μ‐PCy2)2Pt(PHCy2)(H)] (4). When treated with sodium at room temperature, complex 3 transforms into [Pt(μ‐PCy2)(PHCy2)]2(Pt−Pt) (5). The sodium reduction of 1 carried out at room temperature leads to the direct formation of the phosphido bridged dinuclear complex [Pt(μ‐PCy2)(PHCy2)]2(Pt−Pt) (5) along with the mononuclear platinum(II) complex [trans‐Pt(PCy2H)2(PCy2)Cl] (6). Complex 6, which has also been obtained by reaction of 1 with LiPCy2, unambiguously shows by single‐crystal X‐ray diffraction the presence of a pyramidal terminal phosphido ligand. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Multinuclear and Dynamic NMR Study of trans-[Pt(Cl)(PHCy2)2(PCy2)], [Pt(Cl)(PHCy2)3][BF4], [Pt(Cl)(PHCy2)3][Cl], trans-[Pt(Cl)(PHCy2)2{P(S)Cy2}], and trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}]. Influence of Intramolecular PO···H−P and Cl···H−P Interactions on Restricted Rotation about Pt−P Bond. X-ray Structure of trans-[Pt(Cl)(PHCy2

“…10 Dynamic Behavior of 2, 3, and 4. To confirm our assignment of ∆G q predominantly to the rotational process, we decided to compare the dynamic behavior of 1 with that of complexes [Pt(PHCy 2 ) 3 Cl]BF 4 …”

“…All manipulations of complex 1 (prepared as described in ref 10) were carried out under a pure argon atmosphere, using freshly distilled and oxygen-free solvents. Dicyclohexylphosphane (Strem) and PtCl 2 (Acros) were used as received.…”

Synthesis of Heterodimetallic Complexes by Reaction of a Terminal Phosphido Pt Complex with Metal‐Based Nucleophiles and Electrophiles

“…[18] A mixture of 1 and AuCl(PPh 3 ) in a 2:1 molar ratio in thf afforded a white solid, which was characterized as the trinuclear complex trans- [8]Cl (Scheme 6). Synthesis of trans- [8]Cl. Scheme 6.…”

“…[3] Both strategies have been successfully employed for the synthesis of phosphanidobridged heterodinuclear complexes from terminal phos- [ phanido complexes. [7] We have recently described the synthesis [8] and reactivity with chalcogens [9] of trans-[PtCl(PCy 2 )(PHCy 2 ) 2 ] (1). [7] We have recently described the synthesis [8] and reactivity with chalcogens [9] of trans-[PtCl(PCy 2 )(PHCy 2 ) 2 ] (1).…”

“…[7] We have recently described the synthesis [8] and reactivity with chalcogens [9] of trans-[PtCl(PCy 2 )(PHCy 2 ) 2 ] (1). In this paper, the synthesis of [(PHCy 2 ) 2 Pt(μ-PCy 2 )Co(CO) 3 ](Pt-Co) (2), [(PHCy 2 ) 2 Pt(μ-PCy 2 )Mo(CO) 2 Cp](Pt-Mo) (3), [(PHCy 2 ) 2 -Pt(μ-PCy 2 )W(CO) 2 Cp](Pt-W) (4) and [{Cl(PHCy 2 ) 2 Pt(μ-PCy 2 )} 2 Au]Cl ( [8]Cl), phosphanido-bridged complexes synthesized by the reactions of 1 with nucleophilic M(-1) carbonyl metalates (M = Co, Mo, W) and electrophilic Au I species is described. These two strategies should give access to dinuclear complexes in which the bridging phosphanide ligand would subtend (1) or not subtend (2) a platinum-metal bond.…”