Cyanophosphine derivatives: Nitrile or cyanide functionality?

Alexandrine Maraval (1) , Alain Igau (1) , Christine Lepetit (1) , Anna Chrostowska (2) , Jean-Marc Sotiropoulos (2) , G. Pfister-Guillouzo , Bruno Donnadieu (1) , Jean Pierre Majoral (1)

1 LCC - Laboratoire de chimie de coordination
2 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux

Treatment of dicyanophosphines R-P(CN) 2 with 1 equiv of Schwartz's reagent, [Cp 2Zr(H)Cl] n, led: (i) via a substitution reaction to the formation of the stable hydrocyanophosphines R-P(H)CN (R = Me, tBu, Mes*) or (ii) through a hydrozirconation reaction to the synthesis of the aldiminocyanophosphine R-P(CH double bond NZrCp 2Cl)CN (R = N iPr 2). Further addition of 1 equiv of [Cp 2Zr(H)Cl] n to R-P(H)CN (R = Me, tBu, Mes*) gave the primary phosphine R-PH 2 (R = Me) or the aldimino secondary phosphine R-P(H)(CH double bond NZrCp 2Cl) (R = tBu, Mes*) after the hydrozirconation reaction. Interestingly, the dialdiminophosphorus compound R-P(CH double bond NZrCp 2Cl) 2 (R = N iPr 2) was obtained after addition of [Cp 2Zr(H)Cl] n to R-P(CH double bond NZrCp 2Cl)CN (R = N iPr 2). The difference in reactivity observed for the dicyanophosphines R-P(CN) 2 with the metal hydride [Cp 2Zr(H)Cl] n have been studied with the help of experimental analysis (UV-photoelectron spectroscopy, NMR, IR, X-ray) and computational methods.

Domaines: Chimie inorganique; Chimie organique

Alexandrine Maraval, Alain Igau, Christine Lepetit, Anna Chrostowska, Jean-Marc Sotiropoulos, et al.. Cyanophosphine derivatives: Nitrile or cyanide functionality?. Organometallics, 2001, 20 (1), pp.25--34. ⟨10.1021/om000704h⟩. ⟨hal-01566356⟩