The reactions of MoOCl4 with neutral group 15 and 16 ligands and a re-investigation of some N-donor ligand complexes of MoOCl3
The reactions of MoOCl4 with neutral group 15 and 16 ligands and a re-investigation of some N-donor ligand complexes of MoOCl3
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MoOCl4与中性基团15和16配体的反应以及MoOCl3的一些N供体配体配合物的重新研究
DOI：
10.1016/j.poly.2021.115262
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发表时间：
2021
期刊：
影响因子：
2.6
通讯作者：
Greenacre V
中科院分区：
文献类型：
--
作者：
Greenacre V
氧化钼(VI)MoOCl4与中性配体MeCN、Ph3PO、SMe2、Mes(CH2)3SME、SeMe2、PMe3、2，2‘-联吡啶和1，10-菲咯啉反应生成氧钼(V)络合物，经微量分析、红外光谱、紫外可见光谱和X-射线晶体结构分析证实。出乎意料的是，与SeMe2形成的产物为[SeMe3]2[Mo2O2Cl6(μ-Cl)2]，与SMe2形成的产物为[SMe2Cl2]2[Mo2O2Cl6(μ-Cl2)2]。X-射线晶体结构为：[MoOCl3(MeCN)2]、[{MoOCl2(MeCN)}2(µ-Cl)2]、[MoOCl3{Mes(CH2)3Sme}]、[SeMe3][MoOCl4(H2O)]、[SMe2Cl2]2[Mo2O2Cl6(μ-Cl)2]和[PMe3H][MoOCl4(PMe3)]。MoOCl4与[Et4N]Cl反应生成双核Mo(V)物种[Et4N]2[Mo2O2Cl6(μ-Cl)2]。以[MoOCl3(THf)2]和二亚胺为原料合成了红聚体-[MoOCl3(二亚胺)](二亚胺=2，2‘-联吡啶，1，10-菲咯啉)配合物，并对其结构进行了表征。从MoOCl4和二亚胺(以及其他方式)得到的已知的[MoOCl3(二亚胺)]的绿色异构体被认为是与另一个较低氧化态的钼络合物共结晶的红色异构体。
The reaction of molybdenum(VI) oxide tetrachloride, MoOCl4, with neutral ligands including MeCN, Ph3PO, SMe2, MeS(CH2)3SMe, SeMe2, PMe3, 2,2′-bipyridyl and 1,10-phenanthroline, results in reduction to form oxomolybdenum(V) complexes, identified by microanalysis, IR and UV/visible spectroscopy and via X-ray crystal structure analyses of several examples. Unexpectedly, the product formed with SeMe2was [SeMe3]2[Mo2O2Cl6(μ-Cl)2] and with SMe2, [SMe2Cl]2[Mo2O2Cl6(μ-Cl)2]. X-ray crystal structures are reported former-[MoOCl3(MeCN)2], [{MoOCl2(MeCN)}2(µ-Cl)2], [MoOCl3{MeS(CH2)3SMe}], [SeMe3][MoOCl4(H2O)], [SMe2Cl]2[Mo2O2Cl6(μ-Cl)2] and [PMe3H][MoOCl4(PMe3)]. The reaction of MoOCl4with [Et4N]Cl forms the dinuclear Mo(V) species, [Et4N]2[Mo2O2Cl6(μ-Cl)2].The redmer-[MoOCl3(diimine)] (diimine = 2,2′-bipyridyl, 1,10-phenathroline) complexes were prepared from [MoOCl3(thf)2] and the diimine and fully characterised by spectroscopy and by X-ray crystallography. The long-known ‘green isomers’ of [MoOCl3(diimine)] obtained from MoOCl4and the diimines (and in other ways), are suggested to be the red isomers co-crystallised with another lower oxidation state molybdenum complex.