PNacPNacE: (E = Ga, In, Tl) - monomeric group 13 metal(i) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide.
PNacPNacE: (E = Ga, In, Tl) - monomeric group 13 metal(i) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide.
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DOI：
10.1039/c7dt04048b
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发表时间：
2017-12
影响因子：
4
通讯作者：
Christian P. Sindlinger;S. R. Lawrence;Shravan S. Acharya;C. Ohlin;A. Stasch
中科院分区：
文献类型：
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作者：
Christian P. Sindlinger;S. R. Lawrence;Shravan S. Acharya;C. Ohlin;A. Stasch
空间要求较高的双(亚胺基膦酰基)甲烷碱金属配合物LM(L-=HC(Ph2P[双键，长度为m-破折号]NDIP)2-，Dip=2，6-iPr2C6H3；M=Li，Na，K)与“GaI”、InBr3或TlBr3发生盐异构化反应，分别得到单体13族金属(I)配合物Le：，E=Ga(1)，In(2)和Tl(3)，在Ga的情况下生成少量的LGaI24。X-射线单晶衍射法测定了LE：1-3的分子结构，结果表明它们含有带有N，N‘-螯合甲烷配体和双配位金属(I)中心的褶皱六元环。将LAlMe2加碘制备的LAlI25还原反应不成功，到目前为止还没有制备出铝(I)同系物。对LE：，E=Al-Tl进行了密度泛函理论研究，结果表明LE：是一种与13族金属(I)离子配位的阴离子、N，N‘-螯合甲烷配体。E=Al-In分子的同位基态主要来自具有高S特征的金属基孤对。
The salt metathesis reaction of the sterically demanding bis(iminophosphoranyl)methanide alkali metal complexes LM (L- = HC(Ph2P[double bond, length as m-dash]NDip)2-, Dip = 2,6-iPr2C6H3; M = Li, Na, K) with "GaI", InBr or TlBr afforded the monomeric group 13 metal(i) complexes LE:, E = Ga (1), In (2) and Tl (3) in moderate yields, and small quantities of LGaI24 in the case of Ga, respectively. The molecular structures of LE: 1-3 from X-ray single crystal diffraction show them to contain puckered six-membered rings with N,N'-chelating methanide ligands and two-coordinated metal(i) centres. Reduction reactions of LAlI25, prepared by iodination of LAlMe2, were not successful and no aluminium(i) congener could be prepared so far. DFT studies on LE:, E = Al-Tl, were carried out and support the formulation as an anionic, N,N'-chelating methanide ligand coordinating to group 13 metal(i) cations. The HOMOs of the molecules for E = Al-In show a dominant contribution from a metal-based lone pair that is high in s-character.