Institute of Condensed Matter and Nanosciences, MOST - Inorganic Chemistry, Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium.
Dalton Trans. 2013 Apr 21;42(15):5252-7. doi: 10.1039/c3dt32886d. Epub 2013 Mar 8.
Reaction of the deprotonated N-thiophosphorylated thiourea 2-PyNHC(S)NHP(S)(OiPr)2 (HL) with NiCl2 leads to the complex [Ni{2-PyNHC(S)NP(S)(OiPr)2}2] ([NiL2]) with unprecedented 1,5,7-N,N′,S-coordination of the ligand. Recrystallization of [NiL2] from a mixture of CH2Cl2–n-hexane or acetone–n-hexane leads to [Ni(L-1,5,7-N,N′,S)2]·CH2Cl2 and [Ni(L-1,5,7-N,N′,S)2], respectively. The latter complex, in turn, shows a temperature-induced polymorphism. [NiL2] in solution shows a paramagnetic distorted octahedral structure where the metal center is coordinated through the nitrogen atoms of the phosphorylamide and pyridyl group functions, and oxygen atoms of the phosphorylamide unit. Furthermore, in the solid state at low temperature, [Ni(L-1,5,7-N,N′,S)2] is shown from high-frequency EPR measurements to possess an S = 1 ground state with large anisotropy.
去质子化的 N-硫代磷酰化硫脲 2-PyNHC(S)NHP(S)(OiPr)2 (HL) 与 NiCl2 反应，导致配合物 [Ni{2-PyNHC(S)NP(S)(OiPr)2}2] ([NiL2]) 的形成，其中配体具有前所未有的 1,5,7-N,N′,S-配位。[NiL2]从 CH2Cl2-正己烷或丙酮-正己烷的混合物中重结晶，分别得到 [Ni(L-1,5,7-N,N′,S)2]·CH2Cl2 和 [Ni(L-1,5,7-N,N′,S)2]。后者的配合物又表现出温度诱导的多晶型现象。在溶液中，[NiL2]显示出顺磁扭曲八面体结构，其中金属中心通过磷酰胺和吡啶基团的氮原子以及磷酰胺单元的氧原子配位。此外，在低温下的固态中，[Ni(L-1,5,7-N,N′,S)2] 通过高频 EPR 测量显示出具有大各向异性的 S = 1 基态。
