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.
Xie
Jin
J
Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, University of Hong Kong, Pokfulam Road, Hong Kong.
Huang
Jie-Sheng
JS
Zhu
Nianyong
N
Zhou
Zhong-Yuan
ZY
Che
Chi-Ming
CM
D018360:Crystallography, X-Ray; D004563:Electrochemistry; D009682:Magnetic Resonance Spectroscopy; D008665:Metalloporphyrins / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009992:Osmium / Q000737:chemistry*; D019800:Phenol / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*
D008665:Metalloporphyrins; D010720:Phosphines; D009992:Osmium; D019800:Phenol; D012428:Ruthenium; C044646:phosphine