The reaction of two equivalents of (TMEDA)Li[(EPiPr2)(TePiPr2)N] (E = S, Se) with NiBr2(DME) in THF at 23 °C yields homoleptic complexes of heterodichalcogenido PNP ligands Ni[(EPiPr2)(TePiPr2)N]2 (2, E = S; 3, E = Se). Similarly, the complexes Ni[(PiPr2)(EPiPr2)N]2 (4, E = Se; 5, E =Te) are obtained by in situ deprotonation of the neutral monochalcogenides EPiPr2NP(H)iPr2 (E = Se, Te) with nBuLi in THF at −78 °C followed by addition of NiBr2(DME). The complexes 2–5 have been characterised by multinuclear (1H, 31P, 77Se and 125Te) NMR spectroscopy in solution and by X-ray crystallography in the solid state, the results of which show that they all exist as the square planar, trans isomers. Aerosol-assisted chemical vapour deposition (AACVD) of Ni[(SePiPr2)(TePiPr2)N]2 yields crystalline Ni0.51Te films at 450–500 °C, which were analysed by X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS).
在23 °C下,两种等量的(TME
DA)Li[(EPiPr2)(TePiPr2)N](E = S,Se)与NiBr2(
DME)在THF中的反应生成异二
硫杂
环戊二烯基
PNP
配体Ni[(EPiPr2)(TePiPr2)N]2(2,E = S;3,E = Se)的均相配合物。类似地,通过在-78 °C下,在THF中用nBuLi原位脱质子化中性单
硫配体EPiPr2NP(H)iPr2(E = Se,Te),然后加入NiBr2(
DME),得到配合物Ni[(PiPr2)(EPiPr2)N]2(4,E = Se;5,E =Te)。通过溶液中的多核(1H,31P,77Se和125Te)核磁共振光谱和固态X射线晶体学对2-5号配合物进行了表征,结果表明它们都以正交异构体的形式存在。在450-500 °C下,Ni[(SePiPr2)(TePiPr2)N]2的气溶胶辅助
化学气相沉积(
AACVD)生成结晶Ni0.51Te薄膜,通过X射线粉末衍射(XRPD)、扫描电子显微镜