Affiliation:
1. Department of Chemistry Indian Institute of Technology Madras Chennai 600036 India
Abstract
AbstractAzametallacyclopropane‐containing base stabilized borane complexes of group 5 transition metals have been synthesized and their structural aspects have been described. Treatment of Cp* based Ta and Nb chlorides, Cp*TaCl4 and Cp*NbCl4 with [LiBH4 ⋅ THF] followed by addition of ligands, such as 2‐mercaptobenzothiazole, MBT, (C7H5NS2) and 2‐mercaptobenzoxazole, MBO (C7H5NSO) led to the formation of complexes [Cp*M‐[BHS(CH2ENC6H4)(C7H4NSE)] (1: M=Ta, E=S; 2; M=Nb, E=S; 3: M=Ta, E=O; 4; M=Nb, E=O, Cp*=pentamethyl‐η5‐cyclopentadienyl). By means of UV‐vis absorption spectra, the electronic properties of these complexes associated with central metal atoms and heteroatoms (S or O) have been evaluated. In contrast, treatment of Cp*TaCl4 with 2‐mercaptopyridine, MP, (C5H5NS) under the same reaction conditions yielded the agostic σ‐borane Ta complex, [Cp*Ta(H3BNC5H4) (C5H4NS)(η2‐S2)], 5. Unlike 1–4, where the metals interact with boron through bridging sulphur, 5 shows a notable σ‐B−H bond interaction with Ta. All spectroscopic data of 1–5 along with the X‐ray diffraction studies suggest complexes 2, 4, and 5 are base (amine) stabilized borane species. Computational studies based on Density Functional Theory (DFT) also supported this conclusion.
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