Complexes of WOCl4 and WSCl4 with neutral N- and O-donor ligands: Synthesis, spectroscopy and structures
Complexes of WOCl4 and WSCl4 with neutral N- and O-donor ligands: Synthesis, spectroscopy and structures
复制标题
DOI：
10.1016/j.poly.2019.01.044
复制
发表时间：
2019-04-01
期刊：
影响因子：
2.6
通讯作者：
Sutcliffe, Laura
中科院分区：
文献类型：
--
作者：
Greenacre, Victoria K.;Hector, Andrew L.;Sutcliffe, Laura
用WOCl4或WSCl4与配体在无水CH2Cl2溶液中制备了配合物[WOCl4(L)]和[WOCl4(L)]（L = OPPh3, OPMe3，吡啶，2,2'-联吡啶），RWOCl4}(2)(mu-L-L)]和[{WOCl4}(2)(mu-L-L)] (L-L = Ph2P(O)(CH2)(n)P(O)Ph-2 (n = 1,2))，并用微量分析、红外光谱和核磁共振（H-1, P-31 {H-1）光谱对其进行了表征。报道了[WOCl4(OPPh3)], RWOCl4)2(mu-Ph2P(O) (CH2)P(O)Ph-2)]和RWSCl4}(2)(mu-Ph2P(O)(CH2)(2)P(O)Ph-2)]的x射线晶体结构。除2,2′-联吡啶外，其余均为六坐标，中性给体反式为W=0或W=S。光谱数据表明[WOCl4(2,2' -bipy)]和[WSCl4(2.2'-bipy)]是七坐标结构。两系列配合物的结构和光谱数据的比较表明，两个钨（VI）基团之间的刘易斯酸度差异不大。[wOCl(4)(OPMe3)]在溶液中分解得到环状三聚体[W3O3(mu-(O)(3)Cl-6(OPMe3)(3)]，结构为六元W3O3环核，具有非常不对称的氧化桥。本文还报道了钨(V)配合物[WOCl3(2,2′-bipy)]的结构。(C) 2019作者。Elsevier Ltd.出版。
The complexes [WOCl4(L)] and [WOCl4(L)](L = OPPh3, OPMe3, pyridine, 2,2'-bipyridyl), RWOCl4}(2)(mu-L-L)] and [{WOCl4}(2)(mu-L-L)] (L-L = Ph2P(O)(CH2)(n)P(O)Ph-2 (n = 1, 2)) have been prepared from WOCl4 or WSCl4 and the ligands in anhydrous CH2Cl2 solution, and characterised by microanalysis, IR and NMR (H-1, P-31 {H-1)) spectroscopy. X-Ray crystal structures are reported for [WOCl4(OPPh3)], RWOCl4)2(mu-Ph2P(O) (CH2)P(O)Ph-2)] and RWSCl4}(2)(mu-Ph2P(O)(CH2)(2)P(O)Ph-2)]. All, except those of 2,2'-bipyridyl, are six-coordinate with the neutral donor trans to W=0 or W=S. Spectroscopic data suggest that the [WOCl4(2,2'bipY)] and [WSCl4(2.2'-bipy)] are seven-coordinate. Comparison of the structural and spectroscopic data for the two series of complexes indicate little difference in Lewis acidity between the two tungsten(VI) moieties. Decomposition of [wOCl(4)(OPMe3)] in solution gave the cyclic trimer [W3O3(mu-(O)(3)Cl-6(OPMe3)(3)], the structure of which revealed a six-membered W3O3 ring core with very asymmetric oxido-bridges. The structure of the tungsten(V) complex [WOCl3(2,2'-bipy)] is also reported. (C) 2019 The Author(s). Published by Elsevier Ltd.