SYNTHESIS AND CHARACTERIZATION OF TRIMETALLOCENES AND TRIMETALLOCENIUM SALTS
SYNTHESIS AND CHARACTERIZATION OF TRIMETALLOCENES AND TRIMETALLOCENIUM SALTS
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DOI：
10.1021/om00007a054
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发表时间：
1995-07-01
期刊：
影响因子：
2.8
通讯作者：
OHARE, D
中科院分区：
文献类型：
--
作者：
BARLOW, S;MURPHY, VJ;OHARE, D
已经使用二茂铁官能化的锂盐Li+（FcCMe（2）C（5）H（4））-（2; Fc = Fe（eta-C5H5）（eta-C5H4））、Li +{FcC（= CH2）C5H4}（-）（4）和Li+（Fc ″ CH2C5H4）（-）（8; Fc ″ = Fe（eta-C（5）Me（4））制备了一系列三核茂金属和三核茂金属络合物。三二茂铁化合物（FcCMe（2）C（5）H（4））（2）Fe（3）和（FcC（= CH_2）C_5H_4）（2）Fe（5）由中心二茂铁组成。通过单cal连接;（Fc ″ CH_2C_5H_4）（2）M（M = Fe（9），Co（10），Cr（11））的末端是八甲基二茂铁单元。循环伏安实验表明，3和5表现出三个可逆的氧化还原过程，表明在这些配合物中的金属中心之间的显着的静电相互作用。对于9和10，观察到两个氧化还原事件。一系列的反磁性和顺磁性阴离子的三茂鎓盐也已从这些三茂烯合成。变温磁化率数据的顺磁性trixanthenes和trixanthenium盐都遵守居里-外斯定律，没有证据表明显着的自旋-自旋交换金属中心之间的相互作用。合成了电荷转移盐{（Fc "CH_2C_5H_4）（2）Fe}（2+）（TCNE（-））（2）（17; TCNE =四氰基乙烯）和{（Fc" CH_2C_5H_4）（2）Co}（3+）（TCNE（-））（3）（18），并研究了它们的磁性。
A range of trinuclear metallocene and metallocenium complexes have been prepared using the ferrocene-functionalized lithium salts Li+(FcCMe(2)C(5)H(4))- (2; Fc = Fe(eta-C5H5)(eta-C5H4)), Li+{FcC(=CH2)C5H4}(-) (4), and Li+(Fc''CH2C5H4)(-) (8; Fc'' = Fe(eta-C(5)Me(4)H)(eta-C(5)Me(4))). The triferrocenes (FcCMe(2)C(5)H(4))(2)Fe (3) and (FcC(=CH2)C5H4)(2)Fe (5) consist of a central ferrocene. linked by single-cal;bon bridges to two terminal ferrocene units, whereas (Fc''CH2C5H4)(2)M (M = Fe (9), Co (10), Cr (11)) have terminal octamethylferrocene units. Cyclic voltammetry experiments reveal that 3 and 5 exhibit three reversible redox processes, indicating significant electrostatic interactions between the metal centers in these complexes. For 9 and 10 two redox events are observed. A range of metallocenium salts with diamagnetic and paramagnetic anions has also been synthesized from these trimetallocenes. Variable-temperature magnetic susceptibility data on paramagnetic trimetallocenes and trimetallocenium salts all obey the Curie-Weiss law, with no evidence for significant spin-spin exchange interactions between metal centers. The charge-transfer salts {(Fc''CH2C5H4)(2)Fe}(2+)(TCNE(-))(2) (17; TCNE = tetracyanoethylene) and {(Fc''CH2C5H4)(2)Co}(3+)(TCNE(-))(3)(18) have been prepared and their magnetic properties investigated.