Stubenhofer, Markus and Kuntz, Christian and Bodensteiner, Michael and Timoshkin, Alexey Y. and Scheer, Manfred (2013) Versatile Reactivity of Bridged Pentelidene Complexes toward Secondary and Tertiary Phosphines. ORGANOMETALLICS, 32 (12). pp. 3521-3528. ISSN 0276-7333, 1520-6041
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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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PHOSPHORUS TRIPLE BOND; EFFECTIVE CORE POTENTIALS; MAIN-GROUP ELEMENTS; P-RICH PHOSPHANES; TERMINAL PHOSPHINIDENE; MOLECULAR CALCULATIONS; CRYSTAL-STRUCTURE; COORDINATION CHEMISTRY; TRANSITION-METALS; MULTIPLE BONDS; |
| 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: | 07 Apr 2020 11:43 |
| Last Modified: | 07 Apr 2020 11:43 |
| URI: | https://pred.uni-regensburg.de/id/eprint/16492 |
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