Reaction of Pentelidene Complexes with Diazoalkanes: Stabilization of Parent 2,3-Dipnictabutadienes

Seidl, Michael and Stubenhofer, Markus and Timoshkin, Alexey Y. and Scheer, Manfred (2016) Reaction of Pentelidene Complexes with Diazoalkanes: Stabilization of Parent 2,3-Dipnictabutadienes. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 55 (45). pp. 14037-14040. ISSN 1433-7851, 1521-3773

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Abstract

The reaction of the phosphinidene complex [Cp*P{W(CO)(5)}(2)] (1a) with diphenyldiazomethane leads to [{W(CO)(5)}Cp*P=NN{W(CO)(5)}=CPh2] (2). Compound 2 is a rare example of a phosphadiazadiene ligand (R-P=N-N=CRR) complex. At temperatures above 0 degrees C, 2 decomposes into the complex [{W(CO)(5)}PCp*{N(H)N=CPh2)(2)] (3), among other species. The reaction of the pentelidene complexes [Cp*E{W(CO)(5)}(2)] (E=P, As) with diazomethane (CH2NN) proceeds differently. For the arsinidene complex (1b), only the arsaalkene complex 4b [{W(CO)(5)}(2){(1:2)-(Cp*)As=CH2}] is formed. The reaction with the phosphinidene complex (1a) results in three products, the two phosphaalkene complexes [{W(CO)(5)}(2){(1:2)-(R)P=CH2}] (4a: R=Cp*, 5: R=H) and the triazaphosphole derivative [{W(CO)(5)}P(Cp*)-CH2-N{W(CO)(5)}=N-N(N=CH2)] (6a). The phosphaalkene complex (4a) and the arsaalkene complex (4b) are not stable at room temperature and decompose to the complexes [{W(CO)(5)}(4)(CH2=E-E=CH2)] (7a: E=P, 7b: E=As), which are the first examples of complexes with parent 2,3-diphospha-1,3-butadiene and 2,3-diarsa-1,3-butadiene ligands.

Item Type: Article
Uncontrolled Keywords: COORDINATED PHOSPHORUS-COMPOUNDS; PHOSPHINIDENE COMPLEXES; DOUBLE-BOND; ELEMENTS; 1,3-BUTADIENE; HETEROCYCLES; ARSINIDENE; AZIDES; arsenic; 1,3-butadienes; diazomethane; phosphinidenes; phosphorus; tungsten
Subjects: 500 Science > 540 Chemistry & allied sciences
Divisions: Chemistry and Pharmacy > Institut für Anorganische Chemie
Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer
Depositing User: Dr. Gernot Deinzer
Date Deposited: 15 Mar 2019 11:55
Last Modified: 15 Mar 2019 11:55
URI: https://pred.uni-regensburg.de/id/eprint/3966

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