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

Abstract

[Ru II(por)(PH nPh 3-n) 2], [Os II(por)(CO)(PH nPh 3-n)] (n=1, 2), and [Os II(F 20-tpp){P(OH)Ph 2}(PHPh 2)] (F 20-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)O 2] with the respective primary/secondary phosphane and characterized by 1H NMR, 31P NMR, UV/Vis, and IR spectroscopy, mass spectrometry, and elemental analysis. The reac tion of [Os VI(por)O 2] with PHPh 2 also gave minor amounts of [Os II(por){P(OH)Ph 2) 2]. [Ru II(F 20-tpp)(PH 2Ph) 2] exhibits a remarkable stability toward air and shows a reversible metal-centered oxidation couple at E 1/2=0.39 V versus [Cp 2Fe] +/0 in the cyclic voltam mogram. The structures of [Ru IIF 20tpp) (PH 2Ph) 2]·2CH 2Cl 2, [Ru II(4-Cltpp)(PHPh 2) 2]·2CH 2Cl 2 (4-Cl-tpp = 5,10,15,20-tetrakis(p-chlorophenyl) porphyrinato dianion), [Ru IIF 20tpp)(PHPh 2) 2], and [Os IIF 20tpp){P(OH)Ph 2) 2} were determined by X-ray crystallography and feature Ru-P distances of 2.3397(11)-2.3609(9) Å and an Os-P distance of 2.369(2) Å. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.