Tetrathiafulvalene-functionalized phosphine as a coordinating ligand. X-Ray structures of (PPh2)4TTF and [(AuCl)4{(PPh2)4TTF}]
Tetrathiafulvalene-functionalized phosphine as a coordinating ligand. X-Ray structures of (PPh2)4TTF and [(AuCl)4{(PPh2)4TTF}]
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DOI：
10.1039/b106310n
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发表时间：
2002-03
期刊：
影响因子：
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通讯作者：
E. Cerrada;Carmelo Diaz;M. Díaz;M. Hursthouse;M. Laguna;M. Light
中科院分区：
文献类型：
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作者：
E. Cerrada;Carmelo Diaz;M. Díaz;M. Hursthouse;M. Laguna;M. Light
膦(PPh2)4TTf(P4)(1)与金(I)配合物[AUX(THT)](X=Cl，C6F5；THt=四氢噻吩)或[Au(Mes)(AsPh3)](Mes=2，4，6-Me3C6H2)反应生成四核衍生物[(AUX)4P4](X=Cl，2；C6F5，3；Mes，4)。以[Au(Trip)(AsPh3)](Trip=2，4，6-Pri3C6H2)开始的类似反应得到双核衍生物[(AuTrip)2P4](5)。当膦P4与[Cu(MeCN)4]PF6、AgCF3SO3或[Au(Tht)2]CF3SO3按2：1摩尔比反应时，得到[M(P4)2]A(A=PF6，M=Cu，6；A=CF3SO3，M=Ag，7，Au，8)，或者当使用1：1摩尔比时，得到[[M2P4](CF3SO3)2}n(M=Ag，9；Au，10)。报道了新配合物的可见-紫外可见光谱和电化学研究。与自由配体P4(1)的两个可逆氧化反应相比，配合物2-10中发生了两个可逆单电子氧化为单阳离子和双阳离子的可逆单电子氧化反应。化合物1和2的结构经X-射线分析确证。
The phosphine (PPh2)4TTF (P4) (1) reacts with the gold(I) complexes [AuX(tht)] (X = Cl, C6F5; tht = tetrahydrothiophene) or [Au(Mes)(AsPh3)] (Mes = 2,4,6-Me3C6H2) to give tetranuclear derivatives [(AuX)4P4] (X = Cl, 2; C6F5, 3; Mes, 4). The analogous reaction starting with [Au(Trip)(AsPh3)] (Trip = 2,4,6-Pri3C6H2) provides the dinuclear derivative [(AuTrip)2P4] (5). When the phosphine P4 reacts with [Cu(MeCN)4]PF6, AgCF3SO3 or [Au(tht)2]CF3SO3 in a 2∶1 molar ratio, complexes [M(P4)2]A (A = PF6, M = Cu, 6; A = CF3SO3, M = Ag, 7, Au, 8) are obtained, or {[M2P4](CF3SO3)2}n (M = Ag, 9; Au, 10) when 1∶1 molar ratios are used instead. Visible-ultraviolet and electrochemical studies of the new complexes are reported. Two, reversible one-electron oxidations to the mono- and di-cation occur in complexes 2–10 at more positive potentials than the two reversible oxidations exhibited by the free P4 (1) ligand. The structures of 1 and 2 have been confirmed by X-ray analysis.