Cyanophosphine Derivatives:  Nitrile or Cyanide Functionality?

Treatment of dicyanophosphines R−P(CN)2 with 1 equiv of Schwartz's reagent, [Cp2Zr(H)Cl] n , led:  (i) via a substitution reaction to the formation of the stable hydrocyanophosphines R−P(H)CN (R = Me, t Bu, Mes*) or (ii) through a hydrozirconation reaction to the synthesis of the aldiminocyanop...

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Bibliographic Details
Published in:Organometallics 2001-01, Vol.20 (1), p.25-34
Main Authors: Maraval, Alexandrine, Igau, Alain, Lepetit, Christine, Chrostowska, Anna, Sotiropoulos, Jean-Marc, Pfister-Guillouzo, Geneviève, Donnadieu, Bruno, Majoral, Jean Pierre
Format: Article
Language:English
Subjects:
Chemical Sciences
Inorganic chemistry
Organic chemistry
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Summary:Treatment of dicyanophosphines R−P(CN)2 with 1 equiv of Schwartz's reagent, [Cp2Zr(H)Cl] n , led:  (i) via a substitution reaction to the formation of the stable hydrocyanophosphines R−P(H)CN (R = Me, t Bu, Mes*) or (ii) through a hydrozirconation reaction to the synthesis of the aldiminocyanophosphine R−P(CHNZrCp2Cl)CN (R = N i Pr2). Further addition of 1 equiv of [Cp2Zr(H)Cl] n to R−P(H)CN (R = Me, t Bu, Mes*) gave the primary phosphine R−PH2 (R = Me) or the aldimino secondary phosphine R−P(H)(CHNZrCp2Cl) (R = t Bu, Mes*) after the hydrozirconation reaction. Interestingly, the dialdiminophosphorus compound R−P(CHNZrCp2Cl)2 (R = N i Pr2) was obtained after addition of [Cp2Zr(H)Cl] n to R−P(CHNZrCp2Cl)CN (R = N i Pr2). The difference in reactivity observed for the dicyanophosphines R−P(CN)2 with the metal hydride [Cp2Zr(H)Cl] n have been studied with the help of experimental analysis (UV−photoelectron spectroscopy, NMR, IR, X-ray) and computational methods.
ISSN:0276-7333
1520-6041
DOI:10.1021/om000704h