Synthesis and reactivity of new trimethylplatinum(IV) complexes containing chiral Schiff bases as ligands: Crystal structure of (OC-6-44-C)-[PtIMe3{kappa(2)-(R)-Ph2P(C6H4)CH=NC*H(Ph)Me-P,N}]
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Date
2006
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ELSEVIER SCIENCE SA
Abstract
Reaction of the tetranuclear complex [PtIMe3](4) with the ligand (S)- and (R)-Ph2P(C6H4)CH=NC*H(Ph)Me in a 1:4 molar ratio yields the mononuclear neutral complexes in diastereoisomeric mixtures [PtIMe3{K-2-Ph2P(C6H4)CH=NC*H(Ph)Me-P,N}]. Iodide abstraction from mixture with AgBF4 in the presence of pyridine (Py) induces a reductive elimination reaction with loss of ethane, leading to the cationic complex [PtMe(Py) {kappa(2) -Ph2P(C6H4)CH=NC*H(Ph)Me-P,N}[BF4] [C* = (S)-, 3; (R)-, 4]. When this reaction was carried out in the presence of PPh3 a consecutive orthometallation reaction with loss of methane is produced, forming the cationic complex [Pt(PPh3){kappa(3)-Ph2P(C6H4)CH=NC*H(C6H4)Me-C,P,N][BF4], [(S)-, 5; (R)-, 6]. All species were characterised in solution by H-1 and P-31{H-1} NMR spectroscopy, elemental analysis and mass spectrometry.
The crystal structure of the diastereoisomer (OC-6-44-C)-[PtIMe3{kappa(2)-(R)-Ph2P(R)-Ph2P(C6H4)CH=NC*H(Ph)Me-P,N}] has been determined by single-crystal X-ray diffraction. (c) 2005 Elsevier B.V. All rights reserved.
The crystal structure of the diastereoisomer (OC-6-44-C)-[PtIMe3{kappa(2)-(R)-Ph2P(R)-Ph2P(C6H4)CH=NC*H(Ph)Me-P,N}] has been determined by single-crystal X-ray diffraction. (c) 2005 Elsevier B.V. All rights reserved.
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Keywords
trimethylplatinum(IV) complexes, optically active Schiff base complexes, reductive elimination reaction, cyclometallated platinum complexes, INTRAMOLECULAR OXIDATIVE ADDITION, TRANSITION-METAL COMPLEXES, NUCLEAR-MAGNETIC-RESONANCE, ARYL HALOGEN BONDS, C-H BONDS, REDUCTIVE ELIMINATION, PLATINUM COMPLEXES, CATALYTIC-ACTIVITY, HALIDE-COMPLEXES, C,N,N' LIGANDS