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Platinum(II) and Palladium(II) Compounds Containing Chiral Thioimines
Author(s) -
Riera Xavier,
López Concepción,
Caubet Amparo,
Moreno Virtudes,
Solans Xavier,
FontBardia Mercè
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200108)2001:8<2135::aid-ejic2135>3.0.co;2-2
Subject(s) - chemistry , palladium , diastereomer , reactivity (psychology) , orthorhombic crystal system , platinum , ligand (biochemistry) , medicinal chemistry , stereochemistry , chelation , methanol , derivative (finance) , ring (chemistry) , crystal structure , crystallography , catalysis , inorganic chemistry , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology , financial economics , economics
A comparative study of the reactivity of the optically pure thioimine: ( S C )‐(−)‐C 6 H 5 −CH=N−CH(CO 2 Me)−CH 2 −CH 2 − SMe ( 1 ) versus platinum(II) and palladium(II) salts is reported. The reaction of 1 with cis ‐[PtCl 2 (dmso) 2 ] leads to the cycloplatinated derivative ( S C ,R S )‐(+)‐[Pt{C 6 H 4 −CH=N−CH(CO 2 Me)−CH 2 −CH 2 −SMe}Cl] ( 3a ). The absolute configuration of 3a has been established unambiguously by X‐ray diffraction: orthorhombic, with a = 8.979 (4), b = 9.605(9), c = 18.205(6) Å, α = β = γ = 90.0°, space group P 2 1 2 1 2 1 . Compound 3a contains a [6.5.6] tricyclic system generated by the fusion of a phenyl ring, a five‐membered platinacycle and a six‐membered chelate ring formed by the coordination of the nitrogen and sulfur to the platinum. When 1 was treated with Na 2 [PdCl 4 ] in methanol at room temperature a (7.9:1) mixture of the two diastereomers {( S C , R S )‐ 5a and ( S C , S S )‐ 5b } of cis ‐[Pd{C 6 H 5 −CH=N−CH(CO 2 Me)−CH 2 −CH 2 −SMe}Cl 2 ] ( 5 ) was formed. However, when the reaction was performed in the presence of sodium acetate, the activation of the σ(C sp 2 ,phenyl −H) bond took place giving the cyclopalladated complex: ( S C , R S )‐(+)‐[Pd{C 6 H 4 −CH=N−CH(CO 2 Me)−CH 2 − CH 2 −SMe}}Cl] ( 6a ). In 6a , the ligand acts as a monoanionic (C,N,S) − terdentate group. The study of the reactivity of 3a and 6a with PPh 3 is also reported.