Molecular and electronic structures of homoleptic nickel and cobalt complexes with non-innocent bulky diimine ligands derived from fluorinated 1,4-diaza-1,3-butadiene (DAD) and bis(arylimino)acenaphthene (BIAN)
Molecular and electronic structures of homoleptic nickel and cobalt complexes with non-innocent bulky diimine ligands derived from fluorinated 1,4-diaza-1,3-butadiene (DAD) and bis(arylimino)acenaphthene (BIAN)
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DOI：
10.1002/ejic.200600236
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发表时间：
2006-08-07
影响因子：
2.3
通讯作者：
Sundermeyer, Joerg
中科院分区：
文献类型：
--
作者：
Khusniyarov, Marat M.;Harms, Klaus;Sundermeyer, Joerg
合成了含大体积氟代N-取代基的二亚胺配合物[Ni-II（（F）DAD）（2）] 1和[Co-II（（F）DAD）（2）] 2 [（F）DAD = N，N '-bis（五氟苯基）-2，3-二甲基-1，4-二氮杂-1，3-丁二烯]以及具有扩展π体系的二亚胺络合物[NiII-（（F）BIAN）（2）] 3和[Co-I（（F）BIAN）（3）] 4（（F）BIAN =双[N-{3，5-双（三氟甲基）苯基}亚胺基]苊）。化合物4代表迄今为止合成的第一个具有三个双（亚氨基）苊配体的配合物。配合物1-4的分子结构在193 K下用X-射线晶体学测定。络合物1、2和3包含具有自由基单阴离子配体对的二价金属离子，而4最好描述为具有自由基单阴离子形式的两个中性（（F）BIAN）（0）和一个（（F）BIAN）（1-）配体的钴（I）络合物。通过SQUID测量和X-带EPR谱研究了顺磁性钴配合物2和4的电子结构。这两种配合物具有双重基态，电子密度主要位于金属d-轨道。4的双重态-四重态能隙被确定为159 cm（-1）。
The diimine complexes with bulky fluorinated N-substituents [Ni-II((F)DAD)(2)] 1 and [Co-II((F)DAD)(2)] 2 [(F)DAD = N,N'-bis(pentafluorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene] as well as diimine complexes with extended pi system [NiII-((F)BIAN)(2)] 3 and [Co-I((F)BIAN)(3)] 4 ((F)BIAN = bis[N-{3,5-bis(trifluoromethyl)phenyl}imino]acenaphthene) were synthesized. Compound 4 represents the first complex with three bis(imino)acenaphthene ligands synthesized so far. The molecular structures of the complexes 1-4 were determined by X-ray crystallography at 193 K. Complexes 1, 2 and 3 comprise the divalent metal ions with pairs of radical monoanionic ligands, whereas 4 is best described as a cobalt(I) complex with two neutral ((F)BIAN)(0) and one ((F)BIAN)(1-) ligand in the radical monoanionic form. The electronic structures of the paramagnetic cobalt complexes 2 and 4 were investigated by SQUID measurements and X-band EPR spectroscopy. Both complexes possess a doublet ground state, with electron density located mostly in the metal d-orbitals. The doublet-quartet energy gap for 4 was established to be 159 cm(-1).