SYNTHESIS OF TERMINAL VANADIUM(V) IMIDO, OXO, SULFIDO, SELENIDO, AND TELLURIDO COMPLEXES BY IMIDO GROUP OR CHALCOGEN ATOM-TRANSFER TO TRIGONAL MONOPYRAMIDAL V[N3N] (N3N = [(ME3SINCH2CH2)3N]3-)
SYNTHESIS OF TERMINAL VANADIUM(V) IMIDO, OXO, SULFIDO, SELENIDO, AND TELLURIDO COMPLEXES BY IMIDO GROUP OR CHALCOGEN ATOM-TRANSFER TO TRIGONAL MONOPYRAMIDAL V[N3N] (N3N = [(ME3SINCH2CH2)3N]3-)
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DOI：
10.1021/ic00085a038
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发表时间：
1994-03-30
影响因子：
4.6
通讯作者：
DAVIS, WM
中科院分区：
文献类型：
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作者：
CUMMINS, CC;SCHROCK, RR;DAVIS, WM
结晶三锂盐Li 3 [N3 N]（N3 N = [（Me 3SiNCH 2CH 2）3 N]3-）与VCl 4（DME）（DME = 1，2-二甲氧基乙烷）反应得到[N3 N]VCl，产率45%。[N3 N]VCl的结构，由X-射线晶体学测定，是一个扭曲的三角双锥与三个赤道硅烷基氨基和轴向氯和胺供体配体。在戊烷中用Na/Hg还原[N3 N]VCl以>90%的产率提供三角形单锥V[N3 N]。V[N3 N]使环氧丙烷、顺式或反式-2-环氧丁烷、吡啶N-氧化物、一氧化二氮或二甲亚砜脱氧以产生[N3 N]V=O。用S8或硫化乙烯处理V[N3 N]得到[N3 N]V=S，而灰色硒与V[N3 N]反应得到黑色结晶[N3 N]V=Se。PMe 3从[N3 N]V=Se中提取硒，形成Me 3 P =Se并再生V[N3 N]。元素碲不与V[N_3N]反应，但当V[N_3N]在甲苯中真空下与Me_3P =Te反应时，溶液中的[N_3N]V=Te可通过NMR观察到。用V-51 NMR对配合物[N3 N]V=X（X = O，S，Se，Te）进行了表征。位移范围超过1600 ppm，更多的电负性硫族元素产生更大的高场V-51化学位移。V[N3 N]与三甲基甲硅烷基叠氮化物反应得到[N3 N] V= NSiMe 3。[N_3N]V= NSiMe_3也可以通过用Na/Hg还原[N_3N] VN_3，然后用Me_3SiCl处理来制备。V[N3 N]与C_5H_5NNC_6F_5反应生成锈红色的[N3 N]V= NC_6F_5，与三甲基硅基重氮甲烷反应生成[N3 N]V=N-N=CH（SiMe_3）。[N3 N]V=N（p-CH 3C 6 H4）通过将Li 3 [N3 N]的溶液加入到C13 V =N（p-CH 3C 6 H4）的乙醚溶液中来制备。NH基团从2-甲基氮丙啶转移到V[N3 N]，释放丙烯并形成黄色结晶[N3 N]V=NH。[N3 N]V=NH可以去质子化，然后甲硅烷基化，得到[N3 N]V= NSiMe 3。[N_3N]V=NH的结构由X射线晶体学确定。对亚氨基氢进行了定位和提纯，V=N-H单元接近线性（173（6）度），V-N（亚氨基）键长为1.638（6）埃。V-N（胺）键长（2.241（6）埃）与[N3 N]VCl中的键长（2.238（6）埃）相当。[N_3N]V=NH的结构与[N_3N]VCl和V[N_3N ′]（N_3N ′ = [It-BuMe_2SiNCH_2CH_2）_3N]_3-）的结构进行了比较和对比。
The crystalline trilithium salt Li3[N3N] (N3N = [(Me3SiNCH2CH2)3N]3-) reacts with VCl4(DME) (DME = 1,2-dimethoxyethane) to give [N3N]VCl in 45% yield. The structure of [N3N]VCl, as determined by X-ray crystallography, is a distorted trigonal bipyramid with three equatorial silylamido groups and axial chloride and amine donor ligands. Reduction of [N3N]VCl with Na/Hg in pentane provides trigonal monopyramidal V[N3N] in >90% yield. V[N3N] deoxygenates propylene oxide, cis-or trans-2-butene oxide, pyridine N-oxide, nitrous oxide, or dimethyl sulfoxide to produce [N3N]V=O. Treatment of V[N3N] with either S8 or ethylene sulfide gives [N3N]V=S, while gray selenium reacts with V[N3N] to give black crystalline [N3N]V=Se. PMe3 abstracts selenium from [N3N]V=Se, forming Me3P=Se and regenerating V[N3N]. Elemental tellurium does not react with V[N3N], but when V[N3N] is treated with Me3P=Te in toluene under vacuum, [N3N]V=Te can be observed by NMR in solution. The chalcogenide complexes [N3N]V=X(X = O,S,Se,Te) were characterized by V-51 NMR. Shifts ranged over 1600 ppm, with the more electronegative chalcogens producing greater upfield V-51 chemical shifts. V[N3N] reacts with trimethylsilyl azide to give [N3N] V=NSiMe3. [N3N]V=NSiMe3 also could be prepared by reducing [N3N]VN3 With Na/Hg, followed by treatment with Me3SiCl. V[N3N] reacts with C5H5NNC6F5 to give rust-red [N3N]V=NC6F5 and with (trimethylsilyl)diazomethane to give [N3N]V=N-N=CH(SiMe3). [N3N]V=N(p-CH3C6H4) was prepared by adding a solution of Li3[N3N] to C13V=N(p-CH3C6H4) in ether. An NH group transfers from 2-methylaziridine to V[N3N], liberating propylene and forming yellow, crystalline [N3N]V=NH. [N3N]V=NH may be deprotonated and then silylated to give [N3N]V=NSiMe3. The structure of [N3N]V=NH was determined by X-ray crystallography. The imido hydrogen was located and refined; the V=N-H unit is nearly linear (173(6)degrees), and the V-N(imido) bond length is 1.638(6) angstrom. The V-N(amine), bond length (2.241(6) angstrom) is comparable to that in [N3N]VCl (2.238(6) angstrom). The structure of [N3N]V=NH is compared and contrasted with the structures of [N3N]VCl and V[N3N'] (N3N' = [It-BuMe2SiNCH2CH2)3N]3-).