Safin Damir A, Babashkina Maria G, Robeyns Koen, Mitoraj Mariusz P, Kubisiak Piotr, Garcia Yann
Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve (Belgium).
Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakow (Poland).
Chemistry. 2015 Nov 9;21(46):16679-87. doi: 10.1002/chem.201501499. Epub 2015 Oct 1.
The reaction of the N-thiophosphorylated thiourea (HOCH2 )(Me)2 CNHC(S)NHP(S)(OiPr)2 (HL), deprotonated by the thiophosphorylamide group, with NiCl2 leads to green needles of the pseudotetrahedral complex [Ni(L-1,5-S,S')2 ]⋅0.5 (n-C6 H14 ) or pale green blocks of the trans square-planar complex trans-[Ni(L-1,5-S,S')2 ]. The former complex is stabilized by homopolar dihydrogen C-H⋅⋅⋅H-C interactions formed by n-hexane solvent molecules with the [Ni(L-1,5-S,S')2 ] unit. Furthermore, the dispersion-dominated C-H⋅⋅⋅ H-C interactions are, together with other noncovalent interactions (C-H⋅⋅⋅N, C-H⋅⋅⋅Ni, C-H⋅⋅⋅S), responsible for pseudotetrahedral coordination around the Ni(II) center in [Ni(L-1,5-S,S')2 ]⋅0.5 (n-C6 H14 ).
由硫代磷酰胺基团去质子化的N-硫代磷酸化硫脲(HOCH2)(Me)2CNHC(S)NHP(S)(OiPr)2(HL)与NiCl2反应，生成假四面体配合物[Ni(L-1,5-S,S')2]·0.5(n-C6H14)的绿色针状物或反式平面正方形配合物反式-[Ni(L-1,5-S,S')2]的浅绿色块状物。前一种配合物通过正己烷溶剂分子与[Ni(L-1,5-S,S')2]单元形成的同极双氢C-H⋅⋅⋅H-C相互作用得以稳定。此外，以色散为主的C-H⋅⋅⋅H-C相互作用与其他非共价相互作用（C-H⋅⋅⋅N、C-H⋅⋅⋅Ni、C-H⋅⋅⋅S）一起，导致了[Ni(L-1,5-S,S')2]·0.5(n-C6H14)中Ni(II)中心周围的假四面体配位。
