The Synthesis of π,n-Complexes of 1-Thio-1,3-dienes with Chromium Group Metals. The Inner-Sphere Hydrophosphorylation of α-Enethiones
New 1-thio-1,3-diene complexes of chromium(0), molybdenum(0), and tungsten(0) with the biden-tate bonding of unsaturated ligand to the metal’s core via the π-system of the C=C bond and sulfur lone electron pair of heterodiene are obtained. Quantum-chemical calculations reveal geometry, electron stru...
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| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Kazan Federal University
2015-06-01
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| Series: | Учёные записки Казанского университета: Серия Естественные науки |
| Subjects: | |
| Online Access: | http://kpfu.ru/portal/docs/F_1524327229/157_2_est_12_e.pdf |
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| Summary: | New 1-thio-1,3-diene complexes of chromium(0), molybdenum(0), and tungsten(0) with the biden-tate bonding of unsaturated ligand to the metal’s core via the π-system of the C=C bond and sulfur lone electron pair of heterodiene are obtained. Quantum-chemical calculations reveal geometry, electron structure, and formation free energies of these complexes, as well as factors governing the coordination mode. Hydrophosphorylation of the complexes begins from the attack of H-dialkylphosphonate towards the thiocarbonyl group; the generated organometallic α-mercaptophosphonates subsequently undergo the mercaptophosphonate-thiolphospate and thiolphosphate-thionphosphate rearrangements with organ-ophosphorus compounds remaining bound to the metal’s core. |
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| ISSN: | 1815-6169 2500-218X |