Chelating versus bridging bonding modes of N-substituted bis(diphenylphosphanyl)amine ligands in Pt complexes and Co2Pt clusters
作者:Vito Gallo、Piero Mastrorilli、Cosimo F. Nobile、Pierre Braunstein、Ulli Englert
DOI:10.1039/b514787e
日期:——
N-substituted dppa ligands Ph2P-NR-PPh2 [R = -CH2CH2SCH2C6H5 (1), -CH2CH2S(CH2)5CH3 (2), -(CH2)9CH3 (3), -C6H5 (4)] were used for the synthesis of cis-[PtCl2Ph2PN(R)PPh2}] complexes [R = -CH2CH2SCH2C6H5 (5), -CH2CH2S(CH2)5CH3 (6), -(CH2)9CH3 (7), -C6H5 (8)] and heterotrinuclear clusters of formula [PtCo2(CO)7Ph2PN(R)PPh2}] [R = -CH2CH2SCH2C6H5 (9), -CH2CH2S(CH2)5CH3 (10), -(CH2)9CH3 (11), -C6H5 (12)]
N取代的dppa配体Ph2P-NR-PPh2 [R = -CH2CH2SCH2C6H5(1),-CH2CH2S(CH2)5CH3(2),-(CH2)9CH3(3),-C6H5(4)]用于合成顺式[[PtCl2 Ph2PN(R)PPh2}]络合物[R = -CH2CH2SCH2C6H5(5),-CH2CH2S(CH2)5CH3(6),-(CH2)9CH3(7),-C6H5(8)]和异三核簇式[PtCo2(CO)7 Ph2PN(R)PPh2}]的公式[R = -CH2CH2SCH2C6H5(9),-CH2CH2S(CH2)5CH3(10),-(CH2)9CH3(11),-C6H5(12)] 。N上相对大的取代基的存在导致配体的更高的螯合能力。对簇9-11的螯合物和桥接形式之间的平衡进行热力学研究表明,焓形式有利于桥接形式,而熵因子有利于螯合。通过单晶X射线衍射确定5和9的结构。