Chemistry of group 5 metallaboranes with heterocyclic thiol ligands: a combined experimental and theoretical study

Abstract

Thermolysis of [(Cp*Nb)₂(B₂H₆)₂], 1b (Cp* = η⁵-C₅Me₅), with 2-mercaptobenzothiazole, C₆H₄NSCSH (MBT), and 2-mercaptobenzoxazole, C₆H₄NOCSH (MBO), yielded hydrogen substituted compounds 2 and 3 with a general formula [(Cp*Nb)₂(B₂H₆)(B₂H₅L)] (2: L = C₆H₄NSCS and 3: L = C₆H₄NOCS). A similar reaction of 1b with Ph₂Se₂ yielded the monosubstituted derivative [(Cp*Nb)₂(B₂H₆){B₂H₅(PhSe)}], 4. All further efforts towards persubstitution of 1b under various drastic conditions were unfruitful. In parallel, in an effort to find a better synthetic route to the known Ta-aziridine complex [Cp*TaBH(C₇H₄NS₂)CH₂S₂NC₆H₄], Cp*TaCl₄ was treated with a 2-mercaptobenzothiazolyl-based borate ligand Na[H₂B(C₆H₄NSCS)₂]. Surprisingly, the reaction led to the formation of the half-sandwich trichloroaryltantalum(V) complex [Cp*TaCl₃{κ²-N,S-C₆H₄NSCS}], 5, containing a heterocyclic thiol ligand. Using an alternative method complex 5 was isolated in good yield when Cp*TaCl₄ was treated with the potassium salt of 2-mercaptobenzothiazole K[C₆H₄NSCS]. All the compounds were characterized by ¹H, ¹¹B{¹H}, and ¹³C{¹H} NMR spectroscopy, and their structures were unequivocally established by crystallographic analysis.