Zusammenfassung
The reaction of the phosphinidene complex [Cp*P{W(CO)(5)}(2)] (1a) with secondary and tertiary phosphines, respectively, proceeds via W(CO)(5) elimination to form the phosphoranylidene complexes [{W(CO)(5)}(Cp*)P-P(H)Pr-i(2)] (2), [{W(CO)(5)}(Cp*)P-(PMePr2)-Pr-i] (7), and [{W(CO)(5)}(Cp*)P-PEt3] (9). Other novel types of products, the phosphine-coordinated bridged parent phosphinidene complexes ...
Zusammenfassung
The reaction of the phosphinidene complex [Cp*P{W(CO)(5)}(2)] (1a) with secondary and tertiary phosphines, respectively, proceeds via W(CO)(5) elimination to form the phosphoranylidene complexes [{W(CO)(5)}(Cp*)P-P(H)Pr-i(2)] (2), [{W(CO)(5)}(Cp*)P-(PMePr2)-Pr-i] (7), and [{W(CO)(5)}(Cp*)P-PEt3] (9). Other novel types of products, the phosphine-coordinated bridged parent phosphinidene complexes [{W(CO)(5)}(2)(H)P-(PMePr2)-Pr-i] (6a) and [{W(CO)(5)}(2)(H)P-PEt3] (8a), are obtained by elimination of 1,2,3,4-tetramethylfulvene. The latter reaction path is predominantly found for the arsinidene complex [Cp*As{W(CO)(5)}(2)] (1b) to yield [{W(CO)(5)}(2)(H)As-(PHPr2)-Pr-i] (4) upon reaction with (HPPr2)-Pr-i and, with tertiary phosphines, the products [{W(CO)(5)}(2)(H)As-(PMePr2)-Pr-i] (6b) and [{W(CO)(5)}(2)(H)As-PEt3] (8b). If a secondary phosphine coordinates to a bridged parent pentelidene complex, Cp*H elimination occurs to form either HP[(PPr2)-Pr-i{W(CO)(5)}](2) (3) or the phosphine-substituted diarsene complex W(CO)(5)[(AsPPr2)-Pr-i{W(CO)(5)}](2) (5). Each of the new products has been characterized by X-ray structure analysis, NMR, and mass spectroscopy. In each case as a first step the Lewis acid/base adducts are formed, which was monitored by P-31 NMR spectroscopy. The different reaction pathways of the electrophilic pentelidene complexes [Cp*E{W(CO)(5)}(2)] (E = P, As) have been emphasized by extended DFT calculations.
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