Synthesis of phosphido-bridged dinuclear complexes through sodium reduction of cis-[M{P(C6H11)2 H}2Cl2] (M = Ni or Pd)

Synthesis of Phosphido‐Bridged Phosphinito Platinum(I) Complexes by Reaction of cis‐PtCl2(PHCy2)2 with Oxygenated Bases – Crystal Structure of [(PCy2OMe)Pt(μ‐PCy2)]2(Pt–Pt)

“…The sequence of reactions leading from b to [(PCy 2 OR)Pt(µ-PCy 2 )] 2 (Pt-Pt) has already been proposed for the synthesis of several analogous systems. [3,18,28] When R is H, the intramolecular oxidative addition of the P-H bond to Pt is disfavoured by the co-presence in the hypothetically formed Pt(PCy 2 )(H)(PCy 2 OH) of a strongly basic centre (the terminal phosphide) and an acidic proton (Cy 2 POH). Reaction of a with b (R = H, path 2) can give intermediate c, which evolves into the final product 2 after loss of water and ring closure.…”

“…NMR features can help in discriminating between the two structures. We have previously noticed that binuclear monobridged dicyclohexylphosphane complexes of Pd and Pt such as [(Cy 2 PH)(Cl)Pt(µ-PCy 2 )Pt(Cy 2 PH) 2 ]- (Pt-Pt) [3] or [(Cy 2 PH)(Cl)Pd(µ-PCy 2 )Pd(Cy 2 PH) 2 ]-(Pd-Pd) [18] (Supporting Information, ESI 2) are characterised by broad 31 2 showed that each platinum atom is involved in a four-membered Pt-P-O-Pt ring. [19] Finally, equilibrium between structures A and B seems unlikely because the signals found in the 195 Pt{ 1 H} NMR spectrum recorded at 195 K did not differ significantly from those found at 295 K.…”

(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

“…For the related palladium complex 7 the signal of the PHCy 2 ligand trans to the bridging phosphide group is already a broad doublet at room temperature [5] and becomes a very broad singlet by lowering the temperature down to Ϫ38°C ( Figure 2). This is in agreement with a more pronounced fluxionality of palladium with respect to platinum complexes.…”

“…[2] Phosphido-bridged dinuclear metal(I) complexes have been accessed by sodium reduction of Ni(PCy 2 Ph) 2 Cl 2 , [3] Pt(PHtBu 2 ) 2 Cl 2 , [4] and M(PHCy 2 ) 2 Cl 2 (M ϭ Ni, Pd). [5] Moreover, when the sodium reaction of Pd(PHCy 2 ) 2 Cl 2 was carried out at 0°C, the isolation of [(PHCy 2 )(Cl)Pd(µ-PCy 2 )Pd(PHCy 2 ) 2 ](PdϪPd) (7) was achieved (Scheme 1). Scheme 1 In this paper we describe the reactivity of cisPt(PHCy 2 ) 2 Cl 2 (1) towards sodium metal which was found to depend on the reaction temperature.…”

“…Scheme 1 In this paper we describe the reactivity of cisPt(PHCy 2 ) 2 Cl 2 (1) towards sodium metal which was found to depend on the reaction temperature. At 0°C the phosphido-bridged dinuclear platinum species cis-[(PHCy 2 )(H)Pt(µ-PCy 2 )] 2 (2) and [(PHCy 2 )(Cl)Pt(µ-PCy 2 )Pt(PHCy 2 ) 2 ](PtϪPt) (3) were formed, whereas a mixture of [Pt(µ-PCy 2 )(PHCy 2 )] 2 (PtϪPt) (5) and the mononuclear (phosphido)platinum(II) complex [transPt(PHCy 2 ) 2 (PCy 2 )Cl] (6) was obtained when the reaction was carried out at room temperature.…”