SYNTHESIS AND CRYSTALLOGRAPHIC CHARACTERIZATION OF A DINUCLEAR 1,2-HYDRAZIDO(2-) COMPLEX OF TUNGSTEN(VI), [W(ETA-5-C5ME4(TERT-BU))(CCME3)I]2(MU-N2H2).CH2CL2
SYNTHESIS AND CRYSTALLOGRAPHIC CHARACTERIZATION OF A DINUCLEAR 1,2-HYDRAZIDO(2-) COMPLEX OF TUNGSTEN(VI), [W(ETA-5-C5ME4(TERT-BU))(CCME3)I]2(MU-N2H2).CH2CL2
复制标题
DOI：
10.1021/om00079a020
复制
发表时间：
1984-01-01
期刊：
影响因子：
2.8
通讯作者：
SCHROCK, RR
中科院分区：
文献类型：
--
作者：
CHURCHILL, MR;LI, YJ;SCHROCK, RR
前言我们最近报道了一些含有桥联二氮配体的Dinu-Clear Ta配合物的合成。2，3[Ta(CHCMe3)(CH2CMe3)(PMe3)2]2(M-N2)3‘4和[TaCl3(Pbz3)(Thf)]2(µ-2)，5的结晶学研究结果表明，这些分子的Ta^-N=1.8 A，NN？=1.3 A，Ta^-N_2)Ta核最好形式地表示为Ta=NN=Ta体系，而不是Ta-<；-：N=N：-*-Ta体系。所有先前报道的“端-端”桥接氮氮络合物6都被表示为中性氮配体的络合物。因此，[(NH_3)_5Ru~(-)：N=N：-*Ru(NH_3)_(54+)]离子被认为是中性氮的八面体Ru(II)络合物，N=N键长为1.124(15)A，而Ru~*-：N_2距离为1.928(6)A。后一种距离类似于TaCl3(PEt3)(THF)(NPH)中的Ta=N距离。因此，Ta^-N_2)Ta络合物中的µ-2配体可以形式地看作是N_(24~)配体，而络合物则是典型的Ta(V)衍生物。对于同一性为µ-2 2的桥联配体也可能有类似的变化。(注：我们具体考虑的是具有连接性的对称配体HNNH；我们没有考虑NNH2的衍生物。)这样的配体可以作为中性的二亚胺配体(见I)，并且这样-
Introduction We have recently reportedthe synthesis of some dinu-clear complexes of tantalum that contain a bridging dinitrogen ligand. 2, 3 The results of crystallographic studies on [Ta (CHCMe3)(CH2CMe3)(PMe3) 2] 2 (M-N2) 3’4 and [TaCl3 (PBz3)(THF)] 2 (µ-2), 5 which yielded the bond lengths Ta-N= 1.8 A and NN «= 1.3 A, strongly indicate that the Ta^-N2) Ta core of these molecules may best be represented formally as a Ta= NN= Ta system, rather than as a Ta-<—: N= N:—*-Ta system. All previously reported “end-on” bridging dinitrogen complexes6 had been represented as complexes of the neutral dinitrogen ligand. Thus, the [(NH3) 5Ru*-: N= N:-* Ru (NH3) 54+] ion is con-sidered to be an octahedral ruthenium (II) complex of neutral dinitrogen; the N= N bond length is “short”(1.124 (15) A) while the Ru*-: N2 distance is 1.928 (6) A. 7 In contrast to this, the species [TaCl3 (PBz3)()] 2 (µ-2) 5 has a “long” NN bond (1.282 (6) A) and “short" Ta-N bonds (1.796 (5) A); this latter distance is similar to the Ta= N distance foundin TaCl3 (PEt3)(THF)(NPh). 8 The µ-2 ligand in the Ta^-N2) Ta complexes may thus be viewed formally as an N24~ ligand and the complexes as typical Ta (V) derivatives. Similar variations are possible for a bridging ligand of identity µ-2 2.(Note: we are considering specifically a symmetrical ligand with the connectivity HNNH; we are not consideringNNH2 derivatives.) Such a ligand could behave as a neutral diimine ligand (see I), and such be-