Synthesis and structural studies on Ni(II) dithiocarbamates: Exploring intramolecular Ni⋯H-C interactions

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• 作者：Arul Prakasam Balasubramaniam^a ; ^b ; ^{arul7777@yahoo.com} ; Anssi Peuronen^c ; Manu Lahtinen^c ; Muruganandham Manickavachagam^d ; Erkki Kolehmainen^e ; Esa Haapaniemi^e ; Mika Sillanpä ; ä ; ^a
• 关键词：Dithiocarbamate ; X-ray structural analysis ; NMR ; C&ndash ; H⋯Ni interaction ; DFT
• 刊名：Polyhedron
• 出版年：2017
• 出版时间：17 February 2017
• 年：2017
• 卷：123
• 期：Complete
• 页码：453-461
• 全文大小：1810 K
• 卷排序：123

文摘

Five new Ni(II) dithiocarbamates with NiS4, NiS2PN and NiS2PCl coordination spheres, viz. [Ni(bupmbzdtc)2] (1), [Ni(bupmbzdtc)(PPh3)(NCS)] (2), [Ni(bupmbzdtc)(PPh3)Cl] (3), [Ni(4-dpmpzdtc)(PPh3)Cl] (4) and [Ni(pbbzbudtc)(PPh3)(NCS)] (5), where bupmbzdtc = N-butyl(p-methylbenzyl)dithiocarbamato anion, 4-dpmpzdtc = 4-(diphenylmethyl)piperazinecarbodithioato anion, pbbzbudtc = N-(p-bromobenzyl)butyl-dithiocarbamato anion and PPh3 = triphenylphosphine, were synthesized and characterized by UV, IR, NMR and single crystal X-ray diffraction methods. Spectral results suggest a square planar geometry around the Ni(II) metal center for all the synthesized complexes. Single crystal X-ray structural analyses agree to these findings, but also show evidence of intramolecular C–H⋯Ni interactions in complexes 3 and 5 (2.801 and 2.872 Å respectively) in the solid state, analyzed further by computational (DFT) methods. Herein, these and other structural aspects of the homo- (1) and heteroleptic dithiocarbamate complexes (2–5) of Ni(II) are discussed.