Bakthavachalam, K. ; Yuvaraj, K. ; Zafar, Mohammad ; Ghosh, Sundargopal (2016) Reactivity of [M2(μ-Cl)2(cod)2] (M=Ir, Rh) and [Ru(Cl)2 (cod)(CH3CN)2] with Na[H2B(bt)2]: formation of agostic versus borate complexes Chemistry - A European Journal, 22 (48). pp. 17291-17297. ISSN 0947-6539
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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/chem.20...
Related URL: http://dx.doi.org/10.1002/chem.201603480
Abstract
Treatment of [M2(μ-Cl)2(cod)2] (M=Ir and Rh) with Na[H2B(bt)2] (cod=1,5-cyclooctadiene and bt=2-mercaptobenzothiazolyl) at low temperature led to the formation of dimetallaheterocycles [(Mcod)2(bt) 2], 1 and 2 (1: M=Ir and 2: M=Rh) and a borate complex [Rh(cod){κ2-S,S′-H2B(bt)2}], 3. Compounds 1 and 2 are structurally characterized metal analogues of 1,5-cyclooctadiene. Metal–metal bond distances of 3.6195(9) Å in 1 and 3.6749(9) Å in 2 are too long to consider as bonding. In an attempt to generate the Ru analogue of 1 and 2, that is [(Rucod)2(bt)2], we have carried out the reaction of [Ru(Cl)2(cod)(CH3CN)2] with Na[H2B(bt)2]. Interestingly, the reaction yielded agostic complexes [Ru(cod)L{κ2-H,S,S′-H2B(bt)2}], 4 and 5 (4: L=Cl; 5: L=C7H4NS2). One of the key differences between 4 and 5 is the presence of different ancillary ligands at the metal center. The natural bond orbital (NBO) analysis of 1 and 2 shows that there is four lone pairs of electrons on each metal center with a significant amount of d character. Furthermore, the electronic structures and the bonding of these complexes have been established on the ground of quantum-chemical calculations. All of the new compounds were characterized by IR, 1H, 11B, 13C NMR spectroscopy, and X-ray crystallographic analysis.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to John Wiley & Sons, Inc. |
| Keywords: | Agostic Complexes; Borate Complexes; Dimetallaheterocycles; Iridium; Rhodium |
| ID Code: | 108837 |
| Deposited On: | 31 Jan 2018 11:55 |
| Last Modified: | 31 Jan 2018 11:55 |
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