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Published on: December 29, 2016
Cooperative B-H Activation: Ligand Diversity in Groups 6 and 8 Transition Metal κ2-N,E-Chelated Complexes (E = S or
Suvam Saha1, Stutee Mohapatra1, Manish Kumar1
1Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India.
Abstract:
The synthesis, structure, and reactivity of the N-heterocyclic carbene (NHC)-supported κ2-N,S-chelated ruthenium complex [(IMe)(PPh3)Ru{κ2-N,S-(mbz)}2] (IMe = 1,3-dimethylimidazol-2-ylidene, mbz = 2-mercaptobenzothiazolyl (NC7H4S2)), 2 has been established. Complex 2 is generated from the reaction of [Ru(PPh3)2Cl2], 1 with IMe followed by the addition of [(mbz)K]. The room-temperature reaction of 2 with [BH3·THF] led to the formation of the dihydridoborate complex, [(Ph3P)Ru{κ3-H,S,S'-(NH2BSBH2N)(S2C7H4)2}], 3. Further, the synthesis and structure of Cp*-supported κ2-N,S-chelated tungsten complexes, [Cp*W(CO)2{κ2-N,S-(NC7H4S2)}], 5 and [Cp*W(CO)2{κ2-N,S-(NC7H4S2)}{κ2-N,S-(N(CH3)C5H4S)}], 6, generated from the reaction of [Cp*W(CO)3Me], 4 and [Na(H3B-NC7H4S2)] have been described. In a similar fashion, pyridine-2-thiolato/selenolato ligand-supported Cp*-based κ2-N,E-chelated (E = S and Se) tungsten complexes, [Cp*W(CO)2{κ2-N,E-(NC5H4E)}] (7a: E = S (pyridine-2-thiolato), 7b: E = Se (pyridine-2-selenolato)), have been isolated from the reaction of [Cp*W(CO)3Me], 4 and [Na(H3B-NC5H4E)] ligands. The reaction of bulky borane ArFBH2 (ArF = 3,5-bistrifluoromethylbenzyl) with 5 led to the isolation of a borate species, [Cp*W(CO)2{κ2-S,H-(H2ArFB-NC7H4S2)}], 10. The complex [Cp*Mo(CO)2{κ2-N,Se-(NC5H4Se)}], 9 generated from the salt elimination reaction of [Cp*Mo(CO)3Cl], 8 and [K(NC5H4Se)] reacts with [BH3·THF] to yield the borate complex [Cp*Mo(CO)2{κ2-Se,H-(H3B-NC5H4Se)}], 11. To investigate the effect of the ligand diversities on the reactivity of all of the κ2-N,E-chelated complexes, density functional theory (DFT)-based calculations were performed.
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