Reactivity of Quinoline-8-carbaldehyde toward Platina-β-diketone and Acetyl(amine)platinum(II) Complexes. Formation of Acyl(hydroxyalkyl)platinum(IV)
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文摘
The reaction of the platina-尾-diketone [Pt2{(COMe)2H}2(渭-Cl)2] (1) with quinoline-8-carbaldehyde (C9H6NCHO) in MeOH/H2O (Pt/C9H6NCHO = 1/2) leads to the cleavage of the chloride bridges in 1 with acetaldehyde displacement and to the formation of the acetylacyl(hydroxyalkyl)platinum(IV) complex [Pt(COMe)Cl(C9H6NCO-魏N,魏C)(C9H6NCHOH-魏N,魏C)] (3) as a single diastereomer (OC-6-46). Water-assisted activation of the OC鈥揌 bond of one aldehyde and H transfer to the oxygen atom of the second aldehyde occurs. In the presence of sodium methoxide, dehydrochlorination of the platinum starting material affords the dinuclear [Pt2(C9H6NCO-魏N,魏C)2(渭-COMe)2] (4) with acetyl bridges in a head-to-tail fashion. Pyridine or tetrahydrofuran fail to cleave the acetyl bridges, which are readily cleaved by triphenylphosphane to afford the mononuclear [Pt(C9H6NCO-魏N,魏C)(COMe)(PPh3)] (5) with the two acyl groups in cis positions. The reaction of the diacetylbis(amine)platinum(II) complexes [Pt(COMe)2(NH2R)2] (R = CH2Ph (2a), Et (2b)) with quinoline-8-carbaldehyde produced the Schiff base products [Pt(COMe)2(C9H6NCH鈺怤R-魏N,魏N鈥?] (R = CH2Ph (6a), Et (6b)). The complexes have been fully characterized, and X-ray diffraction structures of 3 and 4 are reported.
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