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Primary and Secondary Phosphane Complexes of Metalloporphyrins: Isolation, Spectroscopy, and X‐ray Crystal Structures of Ruthenium and Osmium Porphyrins Binding Phenyl‐ or Diphenylphosphane
Author(s) -
Xie Jin,
Huang JieSheng,
Zhu Nianyong,
Zhou ZhongYuan,
Che ChiMing
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200400996
Subject(s) - chemistry , ruthenium , osmium , nuclear magnetic resonance spectroscopy , metal , crystallography , medicinal chemistry , stereochemistry , nuclear chemistry , catalysis , organic chemistry
[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.