A series of new bis(σ)borate and agostic complexes of group 7 metals have been synthesized and structurally characterized from various borate ligands, such as trihydrobis(benzothiazol-2-yl)amideborate (Na[(H3B)bbza]), trihydro(2-aminobenzothiazolyl)borate (Na[(H3B)abz]), and dihydrobis(2-mercaptopyridyl)borate (Na[(H2B)mp2]) (bbza=bis(benzothiazol-2-yl)amine, abz=2-aminobenzothiazolyl, and mp=2-mercaptopyridyl). Photolysis of [Mn2(CO)10] with Na[(H3B)bbza] formed bis(σ)borate complex [Mn(CO)3(μ-H)2BHNCSC6H4(NR)] (1; R=NCSC6H4). Octahedral complex [Re(CO)2(N3C2S2C12H8)2] (2) was generated under similar reaction conditions with [Re2(CO)10]. Similarly, when [Mn2(CO)10] was treated with Na[(H3B)abz], bis(σ)borate complex [Mn(CO)3(μ-H)2BH(HN2CSC6H4)] (3) and the agostic complex [Mn(CO)3(μ-H)BH(HN2CSC6H4)2] (4) were formed. To probe the potential formation of agostic complexes of the heavier group 7 metals, we carried out the photolysis of [M2(CO)10] with Na[(H2B)mp2] and found that [M(CO)3(μ-H)BH(C5H4NS)2] (5: M=Re; 6: M=Mn) was formed in moderate yield. Complexes 1 and 3 feature a (κ3-H,H,N) coordination mode, whereas 4, 5, and 6 display both (κ3-H,N,N) and (κ3-H,S,S) modes of the corresponding ligands. To investigate the lability of the CO ligands of 1 and 3, we treated the complexes with phosphine ligands that generated novel bis(σ)borate complexes [Mn(μ-H)2(BHNCSC6H4)(NR)(CO)2PL2L’] (R=NCSC6H4; 7 a: L=L’=Ph; 7 b: L=Ph, L’=Me) and [Mn(μ-H)2BHN(NCSC6H4)R(CO)2PL2L’] (R=NCSC6H4; 8 a: L=L’=Ph; 8 b: L=Ph, L’=Me). Complexes 7 and 8 are structural isomers with different coordination modes of the bbza ligand. In addition, DFT calculations were performed to shed some light on the bonding and electronic structures of these complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim