Pogo-Stick Iron and Cobalt Complexes: Synthesis, Structures, and Magnetic Properties.
Pogo-Stick Iron and Cobalt Complexes: Synthesis, Structures, and Magnetic Properties.
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DOI：
10.1021/acs.inorgchem.9b02411
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发表时间：
2019-11
影响因子：
4.6
通讯作者：
Marius Peters;D. Baabe;Miyuki Maekawa;D. Bockfeld;Marc-Kevin Zaretzke;M. Tamm;Marc D. Walter
中科院分区：
文献类型：
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作者：
Marius Peters;D. Baabe;Miyuki Maekawa;D. Bockfeld;Marc-Kevin Zaretzke;M. Tamm;Marc D. Walter
本文较全面地研究了单体半三明治铁、钴咪唑啉-2-亚胺配合物的合成、结构和磁性。[Cp‘m(1，3-bis(2，6-diisopropylphenyl)imidazolin-2-iminato)-I)]2(1-M，M=Fe，Co；Cp’=ImDippNLi]2(ImDippN=μ)与[η5-1，2，4-三叔丁基环戊二烯]2(ImDippN=NimDipp)形成末端半夹心化合物[Cp‘m(NimDipp)](2-M，M=Fe，Co)，可作为半三明治铁、钴亚胺络合物的模型。X-射线衍射分析证实了单腿钢琴凳子的结构主题。配合物2-Co也可以通过[Cp‘Co{N(SiMe3)2}](3-Co)与ImDippNH的酸碱反应合成。用~(57)Fe穆斯堡尔谱(M=Fe)、X-波段EPR谱(M=Co)和固态磁化率测量研究了2-M和3-Co的电磁性质。特别是，中心金属原子在2-Fe中采用高自旋(S=2)态，而钴配合物2-Co代表了Co(II)物种的罕见例子，其配位数不同于6，表现出低自旋到高自旋-交叉(SCO)行为。实验观测得到了密度泛函理论计算的补充。
The synthesis, structures, and magnetic properties of monomeric half-sandwich iron and cobalt imidazolin-2-iminato complexes have been comprehensively investigated. Salt metathesis reactions of [Cp'M(μ-I)]2 (1-M, M = Fe, Co; Cp' = η5-1,2,4-tri-tert-butylcyclopentadienyl) with [ImDippNLi]2 (ImDippN = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) furnishes the terminal half-sandwich compounds [Cp'M(NImDipp)] (2-M, M = Fe, Co), which can be regarded as models for elusive half-sandwich iron and cobalt imido complexes. X-ray diffraction analysis confirmed the structure motif of a one-legged piano stool. Complex 2-Co can also be prepared by an acid-base reaction between [Cp'Co{N(SiMe3)2}] (3-Co) and ImDippNH. The electronic and magnetic properties of 2-M and 3-Co were probed by 57Fe Mössbauer spectroscopy (M = Fe), X-band EPR spectroscopy (M = Co), and solid-state magnetic susceptibility measurements. In particular, the central metal atom adopts a high-spin (S = 2) state in 2-Fe, while the cobalt complex 2-Co represents a rare example of a Co(II) species with a coordination number different from six displaying a low-spin to high-spin spin-crossover (SCO) behavior. The experimental observations are complemented by DFT calculations.