Comparison of Binuclear Phospholyl Chromium Carbonyl Derivatives with their Cyclopentadienyl Analogues: Role of the Phosphorus Atom in Ligand-Metal Bonding

Publication date: Available online 10 May 2019Source: Inorganica Chimica ActaAuthor(s): Xin Wan, Chunrong Feng, Guiming Ren, Xiaohong Chen, Rong Jin, Quan Du, Hao Feng, Yaoming Xie, R. Bruce KingAbstractThe structures and energetics of the binuclear phospholyl chromium carbonyl derivatives (C4H4P)2Cr2(CO)n (n = 6, 5, 4, 3) have been investigated by density functional theory. The lowest energy (C4H4P)2Cr2(CO)n (n = 6, 4, 3) structures are completely analogous to their Cp2Cr2(CO)n analogues with two terminal pentahapto phospholyl rings. However, for the pentacarbonyl (C4H4P)2Cr2(CO)5 the lowest energy structure has a bridging seven-electron donor η5,η1-C4H4P ligand using the phosphorus lone pair in addition to the π-system of the phospholyl ligand as well as a Cr–Cr single bond. Thus, except for the pentacarbonyl the phosphorus lone pair of the phospholyl ligand is seen to play a minor role in the energetically preferred structures of the binuclear phospholyl chromium carbonyl derivatives.Graphical abstract
Source: Inorganica Chimica Acta - Category: Chemistry Source Type: research