Transition-metal-substituted diphosphenes. 8. Synthesis structure, and reactivity of mononuclear complexes of zirconium and hafnium containing the bis(trimethylsilyl)phosphide ligand

Synthesis and Reactivity of the Phospha‐Grignard Reagent Mg(P{SiMe3}2)Br(thf)

“…4 (ii) and -72.4 ppm (iii). Resonances (i) and (iii) are consistent with the previously reported zirconium phosphide species Cp 2 Zr(P{SiMe 3 } 2 )Cl (a; δ P = -108.9 ppm in [D 8 ]toluene) [13] and Cp 2 Zr(P{SiMe 3 } 2 ) 2 (b; δ P = -72.2 ppm in [D 6 ]benzene), [14] demonstrating that 1 is effective as a phosphide transfer reagent. Mass spectral analysis (EI + ) showed molecular ion peaks at m/z = 432 (a) and 575 (b) in addition to a peak at m/z = 478 corresponding to the bromide species Cp 2 Zr(P{SiMe 3 } 2 )Br, to which we attribute the 31 P NMR resonance (ii).…”

Zirconium - Phosphorus Chemistry: Strategies in Syntheses, Reactivity, Catalysis, and Utility

“…[24] Marsh et al reported further studies on oxidative addition of phosphane to Zr II species. [29] [7] Despite the demonstrated lability of the Zr À P bond, one of our early reports revealed insertion chemistry of ZrÀP bonds. The reaction of the complexes [Cp 2 Zr(PR 2 ) 2 ] (R Ph, Cy) with S 8 gave 11.…”

Step-wise sulfurization of stable 1,2-bis(ferrocenyl)diphosphene

“…In the case of the sulfurization reaction of Mes * P=PMes * with elemental sulfur in Et 3 N, the corresponding thiadiphosphirane derivative was obtained exclusively, where the corresponding diphosphene-1-sulfide, Mes * P(S)=PMes * , was generated as an isolable intermediate (6)(7)(8). Similarly, sulfurization reactions of other stable diphosphenes are reported to result in the formation of the corresponding thiadiphosphirane derivatives as a final product (1,(9)(10)(11)(12). On the other hand, we have reported the synthesis of the first stable 1,2-bis(ferrocenyl)diphosphene derivative, Fc P=PFc (1), bearing bulky ferrocenyl groups (Fc = 2,5-bis(3,5-dimethylphenyl)ferrocenyl) as a newly developed unique steric protection groups with a redox-active transition metal (13).…”