A new synthetic entry to phosphinophosphinidene complexes. Synthesis and structural characterisation of the first side-on bonded and the first terminally bonded phosphinophosphinidene zirconium complexes [μ-(1,2∶2-η-^tBu₂PP){Zr(Cl)Cp₂}₂] and [{Zr(PPhMe₂)Cp₂}(η¹-P–P^tBu₂)]

Abstract

The reactions of lithiated diphosphanes with transition metal chlorides constitute a new general entry to phosphinophosphinidene complexes: the reaction of Cp2ZrCl2(Cp = C5H5) with tBu2P-P(SiMe3)Li (molar ratio approximately 1:1) yields [mu-(1,2:2-eta-tBu2P=P)[Zr(Cl)Cp2]2]; the reaction of Cp2ZrCl2 with tBu2P-P(SiMe3)Li (molar ratio approximately 1:2) and an excess of PPhMe2 in DME yields the first terminally bonded phosphinophosphinidene complex, [[Zr(PPhMe2)Cp2](eta1-P-PtBu2)].

Nucleophilic Phosphinidene Complexes: Access and Applicability

“…[21] Salt metathesis and Lewis base stabilization also enabled the synthesis of hafnium phosphinidene [Cp 2 (Me 3 P)Hf=PÀMes*] (6), [22] the terminally bonded phosphinophosphinidene complex [Cp 2 (PhMe 2 P)Zr = P À PtBu 2 ] (7), [23] and the uranium [24] For all of these compounds, bent M = P À R bonding is indicated by 31 P NMR spectroscopic data (6 d = 671, 7 728, 8 71 ppm) and solid-state structures (M-P-C/P 7 115.53 (16), 8 143.7(3) ).…”

Synergistic Binding of Both Lewis Acids and Bases to Phosphinidenes

“…unique reagents have also served as convenient sources of free phosphinidenes. [14] Matheys pioneering work has shown that phosphanylidene-s 4 -phosphoranes are more readily handled if complexed to metal centers, such as [W(CO) 5 ]. [15] Little work has appeared on the binding of other Lewis acids to RP = PR 3 , despite the fact that CF 3 P = PMe 3 yields CF 3 P(BH 3 ) 2 PMe 3 upon addition of BH 3 .…”

Phosphinidene-bridged binuclear complexes

“…The outcome of these reactions was quite sensitive to the substituents at the lithiated diphosphane. Thus, for the t Bu-substituted diphosphane only one of the chloride ligands was replaced, generating the phosphinidene complex 15, in which the P-P t Bu 2 ligand is coordinated in a side-on mode and the P atom displays a non-planar geometry (Scheme 8) [24]. In contrast, the bis(phosphinidene) complex 16 was obtained instead when using the NEt 2 -substituted reagent; moreover, other products were obtained in these reactions when changing the solvent [25].…”