Stepwise Formation of a 1,3-Butadiene Analogue of Mixed Heavier Group 15 Elements

Seidl, Michael and Balazs, Gabor and Timoshkin, Alexey Y. and Scheer, Manfred (2016) Stepwise Formation of a 1,3-Butadiene Analogue of Mixed Heavier Group 15 Elements. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 55 (1). pp. 431-435. ISSN 1433-7851, 1521-3773

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Abstract

The reaction of the phosphinidene complex [Cp*P{ W(CO)(5)}(2)] (1a) with di-tert-butylcarboimidophosphene leads to the P-C cage compound 6 and the Lewis acid-base adduct [Cp*P{W(CO)(5)}(2)(CNtBu)] (2a). In contrast, the arsinidene complex shows a different reactivity. At low temperatures, the arsaphosphene complex [{W(CO)(5)}{eta(2)-(Cp*)As=P(tBu)}{W( CO)(5)}] (3) is formed. At these temperatures, 3 reacts further with a second equivalent of carboimidophosphene to form [{W(CO)(5)}{eta(2)-{(Cp*)(tBu) P} As= P(tBu)}{W(CO)(5)}] (5), probably by the insertion of a phosphinidene unit (tBuP) into an As > C bond. In contrast, at room temperature 3 reacts further by a radical-type reaction to form [{(tBu) P=As-As=P(tBu)}{W(CO) (5)}(4)] (4). Compound 4 is the first example of a neutral, 1,3-butadiene analogue containing only mixed heavier Group 15 elements. It consists of two P=As double bonds connected by arsenic atoms.

Item Type: Article
Uncontrolled Keywords: TERMINAL PHOSPHINIDENE COMPLEX; METAL-CONTAINING HETEROCYCLES; MAIN-GROUP ELEMENTS; P=C BOND-CLEAVAGE; CRYSTAL-STRUCTURE; REACTIVITY; PHOSPHAKETENE; PHOSPHORUS; ISOMERIZATION; DIPHOSPHENES; 1,3-butadiene analogues; arsenic; phosphinidene; phosphorus; tungsten
Subjects: 500 Science > 540 Chemistry & allied sciences
Divisions: Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer
Depositing User: Dr. Gernot Deinzer
Date Deposited: 15 Mar 2019 08:25
Last Modified: 15 Mar 2019 08:25
URI: https://pred.uni-regensburg.de/id/eprint/2559

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