A Pair of Dinuclear Fe(II) Enantiomers: Syntheses and Structures of ΛΔ/ΔΛ‐Bis(Dihydridoborate) Complexes

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{κ³-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 κ²-N,S-chelated iron complex, [(dppe)Fe{κ²-N,S-(mp)}₂] (2), we have isolated and structurally characterized a rare example of dimeric iron bis(dihydridoborate) complex, [Fe{κ³-S,H,H-(H₂BH(mp))}₂]₂, ΛΔ/ΔΛ-3 as pair of enantiomers. Interestingly, these enantiomers ΛΔ/ΔΛ-3 have two trans-[Fe{κ³-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 ΛΔ-3 and ΔΛ-3 show considerable electron donation from the filled σ_B-H bonding orbital to vacant <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics><mml:msub><mml:mi>d</mml:mi> <mml:msup><mml:mrow><mml:mi>z</mml:mi></mml:mrow> <mml:mn>2</mml:mn></mml:msup> </mml:msub> <mml:annotation>${{d}_{{z}^{2}}}$</mml:annotation> </mml:semantics> </mml:math> 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.