Philipps-Universität Marburg, Fachbereich Chemie, Hans-Meerwein Straße, 35043, Marburg.
Dalton Trans. 2011 Feb 7;40(5):1183-8. doi: 10.1039/c0dt01166e. Epub 2010 Dec 20.
Unprecedented imido phthalocyaninato complexes of pentavalent refractory metals [PcM(NR)Cl] (M = Mo, W, Re; R = tBu: 1, 3, 6, Mes: 2, 4, 7 or Ts: 5) have been synthesized by reductive cyclotetramerization of phthalonitrile in the presence of appropriate bis(imido) complexes of Mo, W and Re as templates. While d(1) Mo(V) and W(V) species 1-5 show distinctive EPR spectra corresponding to metal centered radicals with hyperfine coupling of two magnetically non-equivalent nitrogen atoms (4 equatorial and 1 axial N), corresponding d(2) Re(V) compounds 6 and 7 are diamagnetic. [PcMo(NtBu)Cl] 1 crystallizes from 1-chloronaphthalene in the tetragonal space group P4/n. The molecular structure reveals, that the metal center is located above the plane of the equatorial N4 and displaced towards the axial π-donor ligand. Due to the thermodynamic trans effect the Mo-Cl bond trans to the imido group is elongated to about 2.600(2) Å.
前所未有的五价难熔金属亚氨基酞菁配合物[PcM（NR）Cl]（M = Mo，W，Re；R = tBu：1，3，6，Mes：2，4，7 或 Ts：5）已通过在适当的双（亚氨基）配合物的存在下通过酞腈的还原环四聚化合成Mo，W 和 Re 作为模板。虽然 d（1）Mo（V）和 W（V）物种 1-5 显示出对应于金属中心自由基的独特 EPR 光谱，其中具有两个磁不等效氮原子（4 个赤道和 1 个轴向 N）的超精细耦合，但相应的 d（2）Re（V）化合物 6 和 7 是抗磁性的。[PcMo（NtBu）Cl]1 从 1-氯萘中以四方 P4/n 空间群结晶。分子结构表明，金属中心位于赤道 N4 平面上方，并向轴向π供体配体位移。由于热力学的反位效应，亚氨基基团反位的 Mo-Cl 键被拉长至约 2.600（2）Å。
