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Synthesis and Characterization of Bis(sigma)borate and Bis–zwitterionic Complexes of Rhodium and Iridium
Rosmita Borthakur, Anangsha De, Babu Varghese,
Published in Wiley-Blackwell
Volume: 1
Issue: 13
Pages: 3757 - 3761
Building upon the chemistry of Rh–N,S-heterocyclic carbene complex, [(Cp*Rh)(L2)(1-benzothiazol-2-ylidene)], 2 (Cp*=η5-C5Me5; L=C7H4NS2) with various monoboranes-Lewis adducts, we explored the chemistry of 2 with BH3⋅thf at elevated temperature. As a result, mild thermolysis of 2 with BH3⋅thf led to the formation of bis(sigma)borate [(η4-C5Me5H)Rh(η2-H3BL)], 3 and a bis-zwitterionic species [Cp*RhS(BH2L2)], 4 with the concomitant release of BH3⋅bt (bt=benzothiazole). The RhS3C2N2B2 atoms in 4 generates two six membered rings fused by a common Rh−S bond, which may be considered as a bicycle [4.4.0] cage at the rhodium center. In an effort to generate the iridium analogue of 3, reaction of [Cp*IrCl2]2 with Na[H3B(mbt)] (mbt=2-mercaptobenzothiazole) was carried out that produced bis(sigma)borate complex [(η4-C5Me5H)Ir(η2-H3BL)], 1. The solid state X-ray structures of 1 and 3 showed that the Cp*H ligand coordinated to the metal center in a η4-fashion. In compound 3, the methyl group is oriented towards rhodium center, whereas it is away from Ir center in 1. In addition, the DFT computations were performed to shed light on the bonding and electronic structures of these compounds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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