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Organoplatinum(IV) and Palladium(IV) Complexes Containing Intramolecular Coordination Systems Based on the 8-Methylquinolinyl Group (mq), Including Structures of the Cation [Pt(mq)Me2(bpy)]+ (bpy = 2,2‘-bipyridine) and the Palladium(IV) Complexes Pd(mq)MeR{(pz)2BH2} (R = Me, Ph; [(pz)2BH2]- = Bis(pyrazol-1-yl)borate)
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Abstract
Oxidative addition of 8-(bromomethyl)quinoline (mqBr) to PdMeR(bpy) (R = Me, Ph; bpy = 2,2‘-bipyridine) and [PdMeR{(pz)2BH2}]- (R = Me, Ph; [(pz)2BH2]- = bis(pyrazol-1-yl)borate]) has given the first isolable palladium(IV) complexes containing an intramolecular coordination system, [Pd(mq)MeR(bpy)]Br [R = Me (1), Ph (2)] and [Pd(mq)MeR{(pz)2BH2}[R = Me (7), Ph (8)]. The pallada(IV)cyclic complex 
(6) has also been isolated. The first structural analysis of an arylpalladium(IV) complex, Pd(mq)MePh{(pz)2BH2} (8), is reported. Complex 8 occurs as two isomers and the one examined by X-ray crystallography has the fac-PdC3 configuration with the phenyl group trans to the quinoline nitrogen donor. NMR spectra of 8 indicate that the other isomer has the methyl group trans to the quinoline nitrogen donor. Similar geometric isomerism occurs for [Pd(mq)MePh(bpy)]BF4 (4). Structural studies of the dimethylpalladium(IV) complex Pd(mq)Me2{(pz)2BH2} (7) and the platinum(IV) cation in [Pt(mq)Me2(bpy)]BF4·0.75(CH2Cl2) (5) reveal similar structures. The cation [Pd(mq)Me2(bpy)]+ is less stable than the methyl(phenyl)palladium(IV) analogue (2), decomposing in (CD3)2CO by reductive elimination to form ethane and 8-ethylquinoline in 
1:2 ratio, together with the Pd(II) products [Pd(mq)(bpy)]Br and PdBrMe(bpy). A complex mixture of 8-substituted-quinolines (saturated and unsaturated substituents) were obtained as the major products of decomposition of 
(6), consistent with mq···CH2 coupling to give Pd(II) species that undergo further decomposition.
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History
- Published In Issue July 05, 1999
- Received February 23, 1999
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