Flash communication: reactivity of bis(phosphine) ligands with dicobalt octacarbonyl
File(s)
Author(s)
Type
Journal Article
Abstract
A series of bis(phosphine) cobalt carbonyl complexes were prepared and investigated in situ using cyclic voltammetry, 1H, 31P, and 59Co NMR spectroscopy (including DOSY), and IR spectroscopy. X-ray diffraction analysis on isolated single crystals confirmed that complex speciation was highly dependent on the nature of the bis(phosphine) and ligand-to-metal stoichiometry. Reactions of [Co2(CO)8] with 1,2 bis(dicyclohexylphosphino)ethane (DCyPE) and 1,2-bis(diphenylphosphino)benzene (DPPBz) led to disproportionation of the precursor, affording cationic κ2-Co(I) bis(phosphine) complexes with Co(−I) tetracarbonyl cobaltate counteranions. In contrast, ferrocenyl bis(phosphine) ligands 1,1′-bis(diphenylphosphino)ferrocene (DPPF), 1,1′-bis(di-isopropylphosphino)ferrocene (DiPrPF), and 1,1′-bis(dicyclohexylphosphino)ferrocene (DCyPF), displayed different reactivity. DiPrPF and DCyPF appeared to form polymeric species at 1:1 ligand-to-metal ratios but favored the formation of discrete neutral dinuclear complexes of the type [(μ2-L)Co2(CO)6] when 0.5 equiv of ligand was employed. Reaction of [Co2(CO)8] with DPPF yielded a significantly larger molecular assembly. Single-crystal X-ray diffraction revealed an unprecedented metallocyclic structure comprising six cobalt tricarbonyl centers interconnected by four bridging DPPF ligands.
Date Issued
2026-07-17
Date Acceptance
2026-07-10
Citation
Organometallics, 2026
ISSN
0276-7333
Publisher
American Chemical Society (ACS)
Journal / Book Title
Organometallics
Copyright Statement
© 2026 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0 .
License URL
Publication Status
Published online
Date Publish Online
2026-07-17