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The reaction of W(CO)6 with pyOSNa (C5-H4NOSNa) and Et4NCl in MeCN affords a new tungsten(0) complex [Et4N][W(pyS)(CO)4] 1 (Mr.= 536.29).The crystal and molecular structures have been determined by X-ray single-crystal diffraction.Complex 1 crystallizes in the orthorhombic system,space group P212121 with a = 8.2429(5),b = 9.1045(4),c =26.8851(14) (A),β = 90.00°,V= 2017.66(18) (A)3,Z = 4,Dc.= 1.765 g/cm3,μ = 58.51 cm-1,F(000) =1048,the final R = 0.0204 and wR = 0.0400 for 4432 observed reflections with I > 2σ(I).X-ray structure analysis revealed that the molecule is acentric and has large first-order hyperpolarizability (7.2 × 10-30 esu),so it could be an IR second-order nonlinear optical candidate material. 相似文献
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1 INTRODUCTION In 1984, thiolate ligand was successfully introduced into molybdenum carbonyl compound by the reaction of Mo(CO)6 with [Et4N]SR( R = C6H5, But) in a moderate condition[1]. From then on, a series of dinuclear molybdenum(0) carbonyl thiolate compounds have been synthesized and characterized by using a variety of thiolate ligands in our research group. It was found that a planar Mo2S2 unit is in the compound [Et4N]2[Mo2(CO)8(SC6H4-CH_3-p)2][2] (2) and a "butterfly" t… 相似文献
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合成了含Mo(0)的三核化合物(Et4N)2[(CO)4Mo(μ-S)2Mo(μ-S)2Mo(CO)4](Ⅰ)和(Et4N)2[(CO)4Mo(μ-S)2W(μ-S)2Mo(CO)4](Ⅱ),测定了(Ⅰ)的晶体结构.Ⅰ属单斜晶系,空间群P2相似文献
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研究了[{(CO)4_M}_xM′S_4]~(2-)[X=1,2;M=Mo(O),W(O);M′=Mo(Ⅵ),W(Ⅵ)]系列簇合物的共振Raman(RR)光谱及红外(IR)光谱.除了对:v_(c—o),v_(M(Ⅵ)—S(b))[S(b):桥基S],v_(M(Ⅵ)—S(t))[S(t):端基S],v_(M(o)—c),δ_(M(O)—C—O)进行归属外,着重讨论v_(M(O)—S(b)),v_(M(O)-M(Ⅵ))的归属.研究了IR谱中Δv[v_(M(Ⅵ)—S(b))(—v)_(M(O)—S(b))]与M(0)→M(Ⅵ)电荷迁移的关系.RR谱研究结果表明,在[(CO)_(4-)MS_2MoS_2]~(2-),[(CO)_4MoS_2MoS_2Mo(CO)_4]~(2-)中S(b)一M(0)电荷迁移与M(0)-MO(Ⅵ)电荷迁移之间有较明显的相互偶合;在[(CO)_4MS_2WS_2]~(2-)中S(b)→W(Ⅵ)与M(O)→W(Ⅵ)电荷迁移、S(t)→W(Ⅵ)与M(0)→W(Ⅵ)电荷迁移之间也分别存在明显的相互偶合,说明了它们存在强的电子离域.本系列簇合物中二核簇的电子离域程度比三核簇强. 相似文献
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过渡金属体系非线性光学性质计算的ECP基组研究 总被引:1,自引:1,他引:0
有效核势(ECP)方法是计算含有过渡金属体系的电子结构及物理性质的有效方法. 本文比较了一系列典型的ECP基组对计算含过渡金属体系非线性光学性质精度的影响. 分别在HF, MP2和DFT理论水平上对过渡金属元素使用不同的ECP基组, 计算了几个过渡金属有机化合物的静态一阶超极化率β0. 研究结果表明: 使用有效核势计算含过渡金属体系时, 核电子的选取是提高计算精度的前提, ns和np电子应该和nd电子一同作为价电子处理; 对于重原子, 必须考虑自旋-轨道耦合相对论效应. 经过综合评估, 认为使用Stuttgart/Dresden赝势的ECP基组, MHF, 在计算含有过渡金属体系非线性光学性质方面是比较好的基组; Stuttgart RSC 1997和SBKJC VDZ相对而言是较好的基组; 基组Lanl2dz, Hay-Wadt MB (n+1)和Hay-Wadt VDZ (n+1)由于没有考虑自旋-轨道耦合, 计算精确度次之; 而基组CRENBL和CRENBS计算的偏差要大一些, 尤其是CRENBS基组由于价电子选择得太少而导致与实验值的偏差最大. 相似文献
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Reaction of Et4NCl, NaSCH2COOMe and W(CO)6 in MeCN affords a new dinuclear tungsten(0) complex [Et4N]2[W2(CO)8(SCH2COOMe)2] (1). The crystal and molecular structure has been determined by X-ray single crystal diffraction. 1 Crystallized in the triclinic, space group P with a=11.141(7), b=10.267(4), c=10.798(3)(); α=93.96(3), β=96.88(4), γ=114.97(5)°; V=1003()3, Z=1, Dc=1.76 g/cm3, μ=60.1 cm-1, R=0.042 and Rw=0.050 for 2967 independent reflections with I>3.0 σ(I). 1 contains a WS2W planar core with nonbonding W...W distance of 3.9611(5)(), and its IR, 13C NMR, and cyclic voltammetry were measured and discussed. 相似文献
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用新方法合成并测定了含Mo(0)的双核化合物(Et_4N)_2[(CO)_4Mo(μ-S)_2MOS_2](Ⅰ)和(Et_4N)_2[(CO)_4Mo(μ-S)_2WS_2](Ⅱ)的晶体结构.Ⅰ和Ⅱ空间群均为Pbcm,Ⅰ的a=1.8403(2)nm,b=1.1963(1)nm,c=1.3482(1)nm,Z=4,R=0.042;Ⅱ的a=1.8453(2)nm,b=1.2004(2)nm,c=1.3494(3)nm,Z=4,R=0.032,Ⅰ和Ⅱ的阴离子均为以Mo(0)为中心的八面体和以Mo(Ⅵ)(或W)为中心的四面体共边且以μ-S连接,Mo(μ-S)2M(M=Mo,W)共平面.其中Mo—Mo键距为0.2992(2)nm,Mo—W为0.30330(8)nm,并发现其Fourier IR中Mo(0)-Sb键的v=424.3 cm~-1。 相似文献
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经由零价双核钼含SR桥的配合物的氧化反应合成了一系列含各种SR桥的双核钼(Ⅰ)配合物Mo_2-(CO)_(8-n)(μ-SR)_2L_n[R=Bu~t,Ph,Bz(C_6H_5CH_2),CH_2CO_2Et;L=MeCN,PPh_3;n=0,2]。并应用红外光谱、元素分析等进行表征,讨论了新的合成途径。[含MeCN配位体配位到Mo(Ⅰ)上的配合物,Mo_2(CO)_6(SPh)_2(MeCN)_2经X射线结构测定,系属单斜晶系,空间群P2_1/c,a=9.241(2),b=9.330(3),c=15.458(4)A:β=105.77(2)°;V=1283(1)A~3;Z=2;R=0.033。Mo—Mo距离为2.978A,表明其Mo-Mo键的形成,Mo-S键长为2.469A。比较同系物Mo_2(CO)_8(μ-SCH_2CO_2-Et)_2,Mo_2(CO)_6(μ-SCH_2CO_2Et)_2(MeCN)_2和Mo_2(CO)_8(μ-SBu~t)_2的结构,并讨论其结构与化学。 相似文献