Phenylimido derivatives of [Mo6O19]2−: syntheses, X-ray structures, vibrational, electrochemical, 95Mo and 14N NMR studies
Phenylimido derivatives of [Mo6O19]2−: syntheses, X-ray structures, vibrational, electrochemical, 95Mo and 14N NMR studies
复制标题
DOI：
10.1016/0020-1693(94)04110-5
复制
发表时间：
1994-10
影响因子：
2.8
通讯作者：
A. Proust;R. Thouvenot;M. Chaussade;F. Robert;P. Gouzerh
中科院分区：
文献类型：
--
作者：
A. Proust;R. Thouvenot;M. Chaussade;F. Robert;P. Gouzerh
[Mo 6 O 18（NPh）]2−和[Mo 6 O 17（NPh）2]2−都是通过（n-Bu 4 N）2[Mo 6 O 19]与1或2当量的[Mo 6 O 18（NPh）]反应形成的。的Ph 3 P-NPh在吡啶或乙腈中，并已分离为混合物。单晶X射线衍射分析表明，[Mo 6 O 18（NPh）]2-、[Mo 6 O 17（NPh）2]2-和[Mo 6 O 19]2-可以在平均组成为（n-Bu 4 N）2[Mo 6 O 19 −x（NPh）x]的同一晶体中一起发现。测定了x =1.16（样品1）和x =0.92（样品2）的平均阴离子的结构参数。1的晶体数据：a=12.684（4），B=22.750（4），c=19.483（3）σ，β=103.04（2）°，空间群P21/c，Z=4，R=0.048，Rw =0.051，共3846次反射，I = 3σ（I）。2的晶体数据：a= 12.678（2），B=22.645（3），c=19.462（4）π，β=104.16（2）°，空间群P21/c，Z=4，R=0.058，Rw =0.061，I = 3σ（I）.用~（95）Mo和~（14）N NMR谱、拉曼光谱和电化学方法研究了产物在乙腈溶液中的性质。这些技术中的每一种都证实了单和双酰亚胺衍生物与母体物质的存在，并允许测定单个组分的特征和溶液的组成;通过不同方法获得的结果具有合理的一致性。
Both [Mo6O18(NPh)]2−and [Mo6O17(NPh)2]2−species are formed by reaction of (n-Bu4N)2[Mo6O19] with either 1 or 2 equiv. of Ph3PNPh in pyridine or acetonitrile and have been isolated as mixtures. Single-crystal X-ray diffraction analyses have shown that [Mo6O18(NPh)]2−, [Mo6O17(NPh)2]2−and [Mo6O19]2−can be found together in the same crystal of average composition (n-Bu4N)2[Mo6O19−x(NPh)x]. The structural parameters of the averaged anions have been determined forx=1.16 (sample1) andx=0.92 (sample2). Crystal data for1:a=12.684(4),b=22.750(4),c=19.483(3) Å, β=103.04(2)°, space groupP21/c,Z=4,R=0.048 andRw=0.051 for 3846 reflections withI⩾3σ(I). Crystal data for2:a= 12.678(2),b=22.645(3),c=19.462(4) Å, β=104.16(2)°, space groupP21/c,Z=4,R=0.058 andRw=0.061 for 5243 reflections withI⩾3σ(I). The products have been studied in acetonitrile solution by95Mo and14N NMR spectroscopy, Raman spectrophotometry and electrochemistry. Each of these techniques has confirmed the presence of the mono- and bis-imido derivatives together with the parent species, and has allowed both the characteristics of the individual components and the composition of the solution to be determined; the results obtained by the different methods are in reasonable agreement.