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单核、假四面体钴（III）化合物的合成与表征

Synthesis and characterization of mononuclear, pseudotetrahedral cobalt(III) compounds.

作者信息

Kozhukh Julia, Minier Mikael A, Lippard Stephen J

机构信息

Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.

出版信息

Inorg Chem. 2015 Jan 20;54(2):418-24. doi: 10.1021/ic5009279. Epub 2014 Dec 22.

DOI:10.1021/ic5009279
PMID:25531129
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4303325/
Abstract

The preparation and characterization of two mononuclear cobalt(III) tropocoronand complexes, Co(TC-5,5) and Co(TC-6,6), are reported. The cobalt(III) centers exist in rare pseudotetrahedral conformations, with twist angles of 65° and 74° for the Co(TC-5,5 and Co(TC-6,6) species, respectively. Structural and electrochemical characteristics are compared with those of newly synthesized Ga(TC-5,5) and Ga(TC-6,6) analogues. The spin state of the pseudotetrahedral Co(TC-6,6) compound was determined to be S = 2, a change in spin state from the value of S = 1 that occurs in the square-planar and distorted square-planar complexes, Co(TC-3,3) (X = BPh4, BAr'4) and Co(TC-4,4), respectively.

摘要

报道了两种单核钴（III）环冠醚配合物Co(TC - 5,5)和Co(TC - 6,6)的制备与表征。钴（III）中心以罕见的假四面体构象存在，[Co(TC - 5,5)]⁺和[Co(TC - 6,6)]⁺物种的扭转角分别为65°和74°。将其结构和电化学特性与新合成的类似物Ga(TC - 5,5)和Ga(TC - 6,6)进行了比较。假四面体Co(TC - 6,6)化合物的自旋态被确定为S = 2，与分别在平面正方形和扭曲平面正方形配合物Co(TC - 3,3)（X = BPh4，BAr'4）和Co(TC - 4,4)中出现的S = 1的自旋态有所不同。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/cbb152edd6fa/ic-2014-009279_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/30e52a20a116/ic-2014-009279_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/935ff56008da/ic-2014-009279_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/bf157253c0cb/ic-2014-009279_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/3d12d1810e37/ic-2014-009279_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/e741ac014298/ic-2014-009279_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/512e302fb81c/ic-2014-009279_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/cbb152edd6fa/ic-2014-009279_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/30e52a20a116/ic-2014-009279_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/935ff56008da/ic-2014-009279_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/bf157253c0cb/ic-2014-009279_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/3d12d1810e37/ic-2014-009279_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/e741ac014298/ic-2014-009279_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/512e302fb81c/ic-2014-009279_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67bc/4303325/cbb152edd6fa/ic-2014-009279_0005.jpg

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