Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 9, Pages 3640-3648Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201405218
Keywords
agostic interactions; borane; carbene; rhodium; transition metals
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Funding
- Department of Science and Technology, New Delhi, India [SR/SI/IC-13/2011]
- Council of Scientific and Industrial Research (CSIR), India
- University Grants Commission
- IIT Madras
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Building upon our earlier results on the synthesis of electron-precise transition-metal-boron complexes, we continue to investigate the reactivity of pentaborane(9) and tetraborane(10) analogues of ruthenium and rhodium towards thiazolyl and oxazolyl ligands. Thus, mild thermolysis of nido-[(Cp*RuH)(2)B3H7] (1) with 2-mercaptobenzothiazole (2-mbtz) and 2-mercaptobenzoxazole (2-mboz) led to the isolation of Cp*-based (Cp*=(5)-C5Me5) borate complexes 5a,b [Cp*RuBH3L] (5a: L=C7H4NS2; 5b: L=C7H4NOS)) and agostic complexes 7a,b [Cp*RuBH2(L)(2)], (7a: L=C7H4NS2; 7b: L=C7H4NOS). In a similar fashion, a rhodium analogue of pentaborane(9), nido-[(Cp*Rh)(2)B3H7] (2) yielded rhodaboratrane [Cp*RhBH(L)(2)], 10 (L=C7H4NS2). Interestingly, when the reaction was performed with an excess of 2-mbtz, it led to the formation of the first structurally characterized N,S-heterocyclic rhodium-carbene complex [(Cp*Rh)(L-2)(1-benzothiazol-2-ylidene)] (11) (L=C7H4NS2). Furthermore, to evaluate the scope of this new route, we extended this chemistry towards the diruthenium analogue of tetraborane(10), arachno-[(Cp*RuCO)(2)B2H6] (3), in which the metal center possesses different ancillary ligands.
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