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

Abstract

[RuII(por)(PHnPh3-n)2], [OsII(por)(CO)(PHnPh3-n)] (n=1, 2), and [OsII(F20-tpp){P(OH)Ph2}(PHPh2)] (F20-tpp=5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato dianion) were prepared from the reaction of [MII(por)(CO)} (M=Ru, Os) or [OsVI(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 reac tion of [OsVI(por)O2] with PHPh2 also gave minor amounts of [OsII(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 E1/2=0.39 V versus [Cp2Fe]+/0 in the cyclic voltam mogram. The structures of [RuIIF20tpp) (PH2Ph)2]·2CH2Cl2, [Ru II(4-Cltpp)(PHPh2)2]·2CH 2Cl2 (4-Cl-tpp = 5,10,15,20-tetrakis(p-chlorophenyl) porphyrinato dianion), [RuIIF20tpp)(PHPh2) 2], and [OsIIF20tpp){P(OH)Ph2) 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.