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 (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 1 H NMR, 31 P NMR, UV/Vis, and IR spectroscopy, mass spectrometry, and elemental analysis. The reaction 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 2 Ph) 2 ] exhibits a remarkable stability toward air and shows a reversible metal‐centered oxidation couple at E 1/2 =0.39 V versus [Cp 2 Fe] +/0 in the cyclic voltammogram. The structures of [Ru II (F 20 ‐tpp)(PH 2 Ph) 2 ]⋅2CH 2 Cl 2 , [Ru II (4‐Cl‐tpp)(PHPh 2 ) 2 ]⋅2 CH 2 Cl 2 (4‐Cl‐tpp=5,10,15,20‐tetrakis( p ‐chlorophenyl)porphyrinato dianion), [Ru II (F 20 ‐tpp)(PHPh 2 ) 2 ], and [Os II (F 20 ‐tpp){P(OH)Ph 2 } 2 ] were determined by X‐ray crystallography and feature RuP distances of 2.3397(11)–2.3609(9) Å and an OsP distance of 2.369(2) Å.