Primary and secondary phosphane complexes of metalloporphyrins: isolation, spectroscopy, and X-ray crystal structures of ruthenium and osmium porphyrins binding phenyl- or diphenylphosphane

Ru(II)(por)(PH(n)Ph(3-n))2], Os(II)(por)(CO)(PH(n)Ph(3-n))] (n=1, 2), and Os(II)(F20-tpp){P(OH)Ph2}(PHPh2)] (F20-tpp=5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato dianion) were prepared from the reaction of M(II)(por)(CO)] (M=Ru, Os) or Os(VI)(por)O2] with the respective primary/secondary phosphane and characterized by 1H NMR, 31P NMR, UV/Vis, and IR spectroscopy, mass spectrometry, and elemental analysis. The reaction of Os(VI)(por)O2] with PHPh2 also gave minor amounts of Os(II)(por){P(OH)Ph2}2]. Ru(II)(F20-tpp)(PH2Ph)2] exhibits a remarkable stability toward air and shows a reversible metal-centered oxidation couple at E(1/2)=0.39 V versus Cp2Fe](+/0) in the cyclic voltammogram. The structures of Ru(II)(F20-tpp)(PH2Ph)2] x 2CH2Cl2, Ru(II)(4-Cl-tpp)(PHPh2)2] x 2CH2Cl2 (4-Cl-tpp=5,10,15,20-tetrakis(p-chlorophenyl)porphyrinato dianion), Ru(II)(F20-tpp)(PHPh2)2], and Os(II)(F20-tpp){P(OH)Ph2}2] were determined by X-ray crystallography and feature Ru-P distances of 2.3397(11)-2.3609(9) A and an Os-P distance of 2.369(2) A.