Vogel, Ulf and Timoshkin, Alexey Y. and Schwan, Karl-Christian and Bodensteiner, Michael and Scheer, Manfred (2006) The formation of Lewis acid/base stabilised phosphanyltrielanes - A theoretical and experimental study. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 691 (21). pp. 4556-4564. ISSN 0022-328X, 1872-8561
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Theoretical investigations on the thermochemistry and the reaction mechanism of the formation of Lewis acid/base stabilised phosphanyltrielanes D (.) H2EPH2 (.) A (D = Lewis base, A Lewis acid) were conducted. The reactions of EH3 (.) D with A (.) PH3 to form D (.) H2EPH2 (.) A and H-2 (E = B, Al, Ga; D = NH3; A = BH3, Cr(CO)(5)) are all exothermic, regardless of whether donors and acceptors are present or absent. The lithium chloride elimination reactions between EH2Cl (.) D and A (.) PH2Li to give D (.) H2EPH2 (.) A and LiCl are endothermic for donor/acceptor stabilised compounds, if formation of gaseous LiCl is considered. If solid lithium chloride is considered all reactions are strongly exothermic. Studies of the transition state for H-2-elimination reactions between EH3 (.) D and A (.) PH3 to yield D - H2EPH2 - A and H-2 were only successful for E = Al, Ga. In these cases the reaction proceeds via a transition state featuring a five or six-coordinate group 13 element. Different donor molecules do not influence the activation energy of such H-2-elimination reactions, but nevertheless they have an effect on the reaction energy. The synthesis of the Cr(CO)(5) substituted phosphanyltrielanes [(CO)(5)Cr(H-2-PBH2 (.) NMe3))] (3a) and [(CO)(5)Cr(H2PAlH2 (.) NMe(3)A (3b)], as well as of the dinuclear complex [(CO)(8)Cr-2(mu-HPBH2 - NMe3)(2)] (4) are described, the latter as a subsequent reaction product of the photolysis of 3a. All compounds were characterised spectroscopically and by X-ray structure analysis. (c) 2006 Elsevier B.V.. All rights reserved.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | EFFECTIVE CORE POTENTIALS; PHOSPHORUS-BORON BONDS; METAL-METAL BOND; MOLECULAR CALCULATIONS; CATALYZED FORMATION; COMPLEXES; PHOSPHINE; PHOSPHANYLALANE; DENSITY; BORANE; DFT calculations; mechanism; group 13/15 compounds; X-ray structure analysis |
| 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: | 20 Jan 2021 10:31 |
| Last Modified: | 20 Jan 2021 10:31 |
| URI: | https://pred.uni-regensburg.de/id/eprint/33880 |
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