Synthesis, structure, and spectroscopic properties of octahedral complexes of tungsten(VI), -(V), and -(IV) containing 2,6-diphenylphenoxide ligation
Synthesis, structure, and spectroscopic properties of octahedral complexes of tungsten(VI), -(V), and -(IV) containing 2,6-diphenylphenoxide ligation
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含有 2,6-二苯酚连接的钨 (VI)、-(V) 和 -(IV) 八面体配合物的合成、结构和光谱性质
DOI：
10.1021/ic00303a033
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发表时间：
1989
影响因子：
4.6
通讯作者：
J. Huffman
中科院分区：
文献类型：
--
作者：
J. Kerschner;P. Fanwick;I. Rothwell;J. Huffman
钨（VI）配合物11 J-WCl_4（OAr-2，6-Ph_2）_2（1）（OAr-2，6-Ph_2 = 2，6-二苯基苯酚）在THF中用丁二烯镁Mg（C_4H_6）或在甲苯中用硼氢化锂LiBH_4处理时经历总的单电子还原。在前一种情况下，八面体thf加合物WCl 3（OAr-2，6-Ph 2）2（thf）（2）以高产率形成，而LiBH 4还原在1当量的PMe 2 Ph存在下发生以产生WCl 3（OAr-2，6-Ph 2）2（PMe 2 Ph）（3）。2和3都是深红色的顺磁性化合物，通过单晶X射线衍射分析显示，含有反式芳氧氧原子和八面体钨金属中心周围的氯基团的mer排列。在单齿膦存在下，用钠汞齐（2 Na/W）还原WCl 4（OAr-2，6-Ph 2）2的甲苯溶液，导致高产率形成亮橙子色W（IV）衍生物WCl 2（OAr-2，6-Ph 2）2（PMe 2 Ph）2（4a）和WCl 2（OAr-2，6-Ph 2）2（PMePh 2）2（4 b）。4a的结构研究显示该分子具有具有Zrazts-，iran $-，rans-WCl 2 O2 P2核的晶体学反转中心。在光谱学上，可以获得d2分子的良好分辨但接触位移的NMR光谱（4）。这些分子的键合和电子结构进行了讨论，特别是与相关的重要性芳氧基氧-p金属-d-键合。在这方面，还获得了WCl_4（OAr-2，6-Ph_2）_2（1）的固态结构。虽然以前报道过，但本研究中的1的结构并没有遭受早期尝试中明显的溶剂损失和衰变问题。晶体数据如下。对于WC 1402 C36 H26（1），在22 ℃下：a= 11.051（1）A，B= 16.693（3）A，c= 17.515（3）A，A = 95.72（1），Z= 4，d，M= 1.686 g cm-3，空间群为F2，/c。对于WCl_3 O_3C_40 H_（34）（2），在19 ℃时：a= 11.582（2）A，B= 12.099（1）A，c= 24.828（4）A，Z= 4，f_（Mlcd）= 1.628 g cm-3，空间群F2，2，21.对于WC 13 P02 C44 H37（3），在22 ℃下：a= 10.8028（8）A，B= 18.430（2）A，c= 21.746（6）A，λ = 100.80（1），Z= 4，λ = 1.435 g cm-3，空间群为P2}/c，对于WC 12 P202 C52 H48（4 a）：a= 10.687（3）k，B= 11.335（3）A，c= 10.289（2）A，a= 92.30（1），λ = 110.95（1），y= 108.21（1），Z= 1，μ Mlcd= 1.557 g cm-3，空间群PI.
The tungsten (VI) complex riJ-WCl4 (OAr-2, 6-Ph2) 2 (1)(OAr-2, 6-Ph2= 2, 6-diphenylphenoxide) undergoes an overall one-electron reduction on treatment either with magnesium butadiene, Mg (C4H6), in thf or with lithium borohydride, LiBH4, in toluene. In the former case the octahedral thf adduct WCl3 (OAr-2, 6-Ph2) 2 (thf)(2) is formed in high yield, while the LiBH4 reduction takes place in the presence of 1 equiv of PMe2Ph to yield WCl3 (OAr-2, 6-Ph2) 2 (PMe2Ph)(3). Both 2 and 3 are deep red, paramagnetic compounds shown by single-crystal X-ray diffraction analyses to containtrans-aryloxide oxygen atoms and a mer arrangement of chloride groups about the octahedral tungsten metal center. Reduction of toluene solutions of WCl4 (OAr-2, 6-Ph2) 2 with sodium amalgam (2 Na/W) in the presence of monodentate phosphines leads to the formation of the bright orange W (IV) derivatives WCl2 (OAr-2, 6-Ph2) 2 (PMe2Ph) 2 (4a) and WCl2 (OAr-2, 6-Ph2) 2 (PMePh2) 2 (4b) in high yields. A structural study of 4a shows the molecule to possess a crystallographic inversion center with a Zrazts-, iran $-,< rans-WCl202P2 core. Spectroscopically, well-resolved but contact-shifted NMR spectra can be obtained for the d2 molecules (4). The bonding and electronic structure of these molecules are discussed, particularly with relevance to the importance of aryloxide oxygen-p to metal-d-bonding. In thisregard, the solid-state structure of WCl4 (OAr-2, 6-Ph2) 2 (1) has also been obtained. Although reported previously, the structure of 1 in the present study does not suffer from some of the solvent loss and decay problems evident in the earlier attempt. Crystal data are as follows. For WC1402C36H26 (1) at22 C: a= 11.051 (1) A, b= 16.693 (3) A, c= 17.515 (3) Á, ß= 95.72 (1), Z= 4, d „M= 1.686 g cm" 3 in space group F2,/c. For WCl3O3C40H34 (2) at 19 C: a= 11.582 (2) A, b= 12.099 (1) A, c= 24.828 (4) A, Z= 4, ífMlcd= 1.628 g cm" 3 in space group F2, 2, 21. For WC13P02C44H37 (3) at22 C: a= 10.8028 (8) A, b= 18.430 (2) A, c= 21.746 (6) A, ß= 100.80 (1), Z= 4,/1= 1.435 g cm'3 in space group P2}/c, For WC12P202C52H48 (4a): a= 10.687 (3) k, b= 11.335 (3) A, c= 10.289 (2) A, a= 92.30 (1), ß= 110.95 (1), y= 108.21 (1), Z= 1,¿ Mlcd= 1.557 g cm" 3 in space group PI.