Complexation of o-(ethylphenylphosphino)(ethylthio)benzene towards nickel(II), palladium(II), and platinum(II) complexes

Article abstract of DOI:10.1080/10426509608029639

Complexation of a hybrid P - S ligand o-(ethylphenylphosphino)(ethylthio)benzene (2) with NiCl₂· DME (DME = MeOCH₂CH₂OMe), (CH₃CN)₂PdCl2, and (CH₃CN)₂PCl₂ provided {o-C₆H₄ (PEtPh)(SEt)-P,S}MCl₂ {3a, M = Ni; 3b, M = Pd, 3c, M = Pt} respectively. Due to the stereogenic center at phosphorus atoms, complexes 3a-c exist as a pair of geometrical isomers, which would interconvert to each other by inversion at the sulfur center. Substitution of chloride by triphenylphosphine occurs in complexes 3b-c to provide [{o-C₆H₄(PEtPh)(SEt)-P,S}M(PPh3)Cl]Cl {4b, M = Pd; 4c, M = Pt}, but not in 3a. Both triphenylphosphine substituted complexes 4b and 4c readily undergo S-dealkylation to give {o-C₆H₄(PPhEt)(S)-P, S}MCl(PPh₃) {5b, M = Pd; 5c, M = Pt} respectively. The inversion barriers (kJ/mol) of coordinated sulfur centers were determined by NMR spectroscopy: 52 ± 2 for 3a, 60 ± 2 for 3b, 70 ± 2 for 3c, 53 ± 2 for 4b and 58 ± 3 for 4c. During dealkylation of [{o-C₆H₄(PEtPh)(SEt)-P, S}Pt(PPh₃)Cl]Cl (4c) with chloride in refluxing chloroform, side product cis-[o-C₆H₄(PPhEt)(S)]₂Pt (6c) was formed. Crystal structures of 3a-c, Sb-c, 6c and [{o-C₆H₄(PEtPh)(SEt)-P,S{Pd(PPh₃)Cl]PF ₆ (4b') were determined.

Full text of DOI:10.1080/10426509608029639

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Phosphorus, Sulfur, and Silicon and
the Related Elements
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COMPLEXATION OF o-
(ETHYLPHENYL-PHOSPHINO)
(ETHYLTHIO)BENZENE TOWARDS
NICKEL(II), PALLADIUM(II), AND
PLATINUM(II) COMPLEXES
Duen-Ren Hou a , Tu-Chen Lin a , Tung-Ying Hsieh a , Ming-
Chu Cheng a , Shie-Ming Peng a & Shiuh-Tzung Liu a
a Department of Chemistry , National Taiwan University ,
Taipei, Taiwan, 106, Republic of China
Published online: 24 Sep 2006.
To cite this article: Duen-Ren Hou , Tu-Chen Lin , Tung-Ying Hsieh , Ming-Chu Cheng ,
Shie-Ming Peng & Shiuh-Tzung Liu (1996) COMPLEXATION OF o-(ETHYLPHENYL-PHOSPHINO)
(ETHYLTHIO)BENZENE TOWARDS NICKEL(II), PALLADIUM(II), AND PLATINUM(II) COMPLEXES,
Phosphorus, Sulfur, and Silicon and the Related Elements, 108:1-4, 61-73, DOI:
10.1080/10426509608029639
To link to this article: http://dx.doi.org/10.1080/10426509608029639
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