In our effort to establish a direct synthetic approach for bis(dihydridoborate) complexes of first-row transition metals, we have investigated the reactivity of [Cp*Fe(dppe)Cl] (dppe =1,2-bis(diphenylphosphino)ethane) with Na[BH3L] (L =2-mercaptopyridine (mp) and 2-mercaptobenzothiazole (mbz)) that led to the formation of iron(II) dihydridoborate complexes, [Cp*Fe{kappa 3-S,H,H-(H2BH(L))}] 1 a-b (L=mp (1 a) and L=mbz (1 b)). Further, in an attempt to isolate the bis(dihydridoborate) complex of iron by the insertion of borane into the kappa 2-N,S-chelated iron complex, [(dppe)Fe{kappa 2-N,S-(mp)}2] (2), we have isolated and structurally characterized a rare example of dimeric iron bis(dihydridoborate) complex, [Fe{kappa 3-S,H,H-(H2BH(mp))}2]2, Lambda Delta/Delta Lambda-3 as pair of enantiomers. Interestingly, these enantiomers Lambda Delta/Delta Lambda-3 have two trans-[Fe{kappa 3-S,H,H-(H2BH(mp))}2] moieties bridged through sulfur atoms of 2-mercaptopyridinyl ligands, where the iron centres are hepta-coordinated. The natural bond-orbital (NBO) analyses of Lambda Delta-3 and Delta Lambda-3 show considerable electron donation from the filled sigma B-H bonding orbital to vacant dz2 \${{d}_{{z}<\^>{2}}}\$ orbital of iron with a substantial contribution from the hydrogen atoms. The localized orbital bonding analysis (LOBA) method suggests that all the iron centres are in +2 oxidation state.

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