A Pair of Dinuclear Fe(II) Enantiomers: Syntheses and Structures of ΛΔ/ΔΛ‐Bis(Dihydridoborate) Complexes
Year: 2024
Type: article
Abstract: 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 σB‐H bonding orbital to vacant 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.
Source: Chemistry - A European Journal
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: bronze
Funders: Indian Institute of Science, Department of Science and Technology, Ministry of Science and Technology, India, Indian Institute of Technology Madras, Indian Institute of Science Education and Research Pune, Indian Institute of Science Education and Research Mohali, Science and Engineering Research Board
Award: G5448675124
OpenAlex ID: W4405289450