室温下将[Fe(NCMe)6 ] 2+和亚磷酸三甲酯在乙腈中的溶液混合形成的红色可溶性物质已鉴定为低自旋[Fe(NCMe)4 {P(OMe)3 } 2 ] 2+来自停止流分光光度动力学研究。提出了一种通过外层复合物形成的交换机制,该交换机制的相对较慢的交换步骤在297±0.1 K时k i = 1.03±0.10 s –1,这是通过P(OMe)进行空间控制的结果。3。随后的反应涉及[Fe(NCMe)6– n {P(OMe)的形成3 } n ] 2+( n = 3或4)要慢得多。三取代阳离子的形成在[P(OMe) 3 ]中是一阶的。
Preparation of the solvated iron(II) cation in acetonitrile using high oxidation-state fluorides and its reaction with trimethyl phosphite
作者:Christopher J. Barbour、James H. Cameron、John M. Winfield
DOI:10.1039/dt9800002001
日期:——
cation [Fe(NCMe)6]2+ is formed from reactions in acetonitrile of iron metal with WF6, MoF6, PF5, or the NO+ cation and from the reaction of iron(II) fluoride with PF5. Oxidation to FeIII is not observed using binary fluorides or NO+, but [Fe(NCMe)6]2+ is oxidised by chlorine in MeCN to give the tetrachloroferrate(III) anion. The MeCN co-ordinated to FeII is replaced by trimethylphosphite giving [Fe(NCMe)P(OMe)3}5]2+