In a quest for effective synthetic precursors for the preparation of B-agostic complexes of ruthenium, we have shown that the reaction of [Cp∗RuCl2]2 (Cp∗ = η5-C5Me5) with [NaBt] or [NaBo] (Bt = dihydrobis(2-mercaptobenzthiazolyl)borate; Bo = dihydrobis(2-mercaptobenzoxazolyl)borate) led to the formation of B-agostic complexes [Cp∗RuBH2L2], 1a,b (1a: L = 2-mercaptobenzthiazol, 1b: L = 2-mercaptobenzoxazol) and [Cp∗RuBH3L], 2a,b (2a: L = 2-mercaptobenzthiazol, 2b: L = 2-mercaptobenzoxazol) in good yields. In parallel to the formation of 1a,b and 2a,b, this method also allowed the formation of ruthenium hydrotrisborate complexes [Cp∗RuBYL3], 3a-c (3a: L = 2-mercaptobenzthiazol, Y = H; 3b: L = 2-mercaptobenzoxazol, Y = H; 3c: L = 2-mercaptobenzoxazol, Y = Cl). The key feature of complexes 3a-c is the coordination of one of the 2-mercaptobenzothiazole ligand that connects to the metal and the boron centre through a common sulfur atom. Upon heating, compounds 3a,b change into their corresponding S→N linkage isomers, in which the boron atom is bonded to three nitrogen atoms. The cyclic voltammetric studies on compounds 3a-c and 4a,b suggest that a deviation in coordination of the ligand change the oxidation potential of the metal centre. All the new compounds have been characterized in solution by 1H, 11B and 13C NMR spectroscopy, mass spectrometry and the structural types of 3a-c and 4b were unequivocally established by crystallographic analysis. © 2015 Elsevier B.V. All rights reserved.