Abstract
The diphosphine, N‐heterocyclic phosphenium/phosphido (NHP+)/(NHP–)‐containing ligand (PPP+/–) has been coordinated to rhodium to study the coordination chemistry of group 9 metals and NHP+/– fragments. Addition of the chlorophosphine ligand PPClP to [Rh(COD)Cl]2 produces the complex (PPClP)RhCl (2), which can be reduced to form (PPP)Rh(PMePh2) (3), the asymmetric dimer [(PPP)Rh]2 (4), and the asymmetric dimer [(PPP)Rh(CNtBu)]2 (5). Analysis of the solid‐state structures and computational studies have provided insight into the electronic structure and bonding in 3–5, revealing that the NHP+/– fragments in 3, 4, and 5 are best described using an NHP–/RhI description. Both 3 and 5 were found to be reactive towards the S–H bond of thiophenol, generating (PPP)RhSPh (6) and (PPP)Rh(SPh)(CNtBu) (7), respectively.
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