Studies of Ruthenium(II) Porphyrins Containing Tertiary Diphosphine Ligands, Including the Crystal Structure of (5,10,15,20-Tetraphenyl¬porphinato)bis(bis(diphenylphosphino)methane)ruthenium(II) Dichloromethane
Ball, R.G., Domazetis, G., David Dolphin, James, B.R., and Trotter, J.
Ru(porp)(PP)2 [H2porp = octaethylporphine (OEP), tetraphenylporphine (TPP); PP = Ph2P(CH2)nPPh2 (n = 1, 2), Ph2P(CH2)2NEt(CH2)2PPh2] were prepared in high yields from Ru(porp)(CO)(EtOH). The crystal structure of Ru(TPP)(Ph2PCH2PPh2)2 shows six-coordinate Ru situated in the porphyrin plane and coordinated to two axial monodentate phosphine ligands, which each have a free dangling P donor. Ru(porp)(PP)2 (n = 2) almost certainly has the same structure and is the first reported case of a compound contging this common diphosphine in a monodentate fashion. The 31P NMR spectra of the Ru(porp)[Ph2P(CH2)nPPh2]2 compdound indicate further structures in solution, including species with a chelated diphosphine. An isolated Ru(OEP)[Ph2P(CH2)4PPh2] complex is likely a polymer incorporating diphosphine bridges.