某些V/S,V/Fe/S和Mn/O簇合物溶液化学行为的NMR研究

STUDY ON SOLUTION CHEMISTRY OF SOME V/S, V/Fe/S AND Mn/O CLUSTER COMPOUNDS BY NMR SPECTROSCOPY

报道我们对某些V/S ,V/Fe/S和Mn/O簇合物溶液化学的核磁研究 .(Et4N) [V4S4(C4H8NCS2 ) 6](1 )的1 HNMR谱包含三个宽峰 ,δ4.77,5.1 7和 7.57,分别归属为端基与桥基配体的α H .游离配体信号的出现表明了溶液中发生配体与溶剂分子的交换反应 .对一系列 [VFe3S4(R2 NCS2 ) 4 ]- 簇合物 (R2 =OC4H8(2 ) ,Et2 (3) )进行了1 HNMR表征 .钒与三个铁中心的配体氢谱被分别归属 .对NMR谱的时间跟踪发现位于δ1 9.6(2 )以及δ34.2(3)的信号逐渐增长 ,这意味着新物种形成 .合成反应的动态NMR跟踪指认了新物种为Fe4S4(R2 NCS2 ) 4 .提出了溶液中簇骼金属原子交换机理 .包含H2 O和NO3配体的单核锰bpy配合物 (4)的氢谱指示出这些单齿配体的可交换性 .它促使配合物 4成为含有两个单核Mn分子的包容化合物 .

This paper reports some interesting prollemsion solution chemistry of V/S,V/Fe/S and Mn/O cluster compounds by their NMR studies.\;The \{\}\+1H NMR spectrum of \[V\-4S\-4(C\-4H\-8NCS\-2)\-6\]\+- shows three broad resonances at 4.77, 5.17 and 7.57ppm which were assigned to the α H of C\-4H\-8NCS\-2 ligands in terminal and bridged ligations. The signals of free C\-4H\-8NCS\-2 are also observed, which occur from an exchange between the R\-2NCS\-2 ligand and the solvent molecules.\;The \{\}\+1H NMR spectra of a series of \[VFe\-3S\-4(R\-2NCS\-2)\-4\]\+- were determined in DMSO d\-6, exhibiting two sets of signals assigned to the α H of the R\-2NCS\-2 ligands linking to V and Fe sites, respectively. A broad peak centered at 19.6ppm for complex 2 or at 33ppm for 3 was found to grow up with time going on, indicating the formation of Fe\-4S\-4(R\-2NCS\-2)\-4(R\-2=OC\-4H\-8,Et\-2). This assignment was identified by a dynamic tracing \{\}\+1H NMR experiment in which Fe\-4S\-4(R\-2NCS\-2)\-4 was synthesized and its \{\}\+1H NMR signals were monitored. A possible metal exchange accompanying the formation of Fe\-4S\-4(R\-2NCS\-2)\-4 in DMSO solution was suggested.\;The \{\}\+1H NMR spectrum of mononuclear Mn bpy complex 4 containing H\-2O and NO\-3 ligands was determined, indicating the exchangeability of these monodentate ligands, which makes 4 become an inclusion compound including two mononuclear Mn molecules. \;