由[Co2（CO）8]溶剂热合成钴-五氯苯酚钳形配合物。

IF 1.7 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Monatshefte Fur Chemie Pub Date : 2023-01-01 Epub Date: 2023-09-09 DOI:10.1007/s00706-023-03123-x

Heiko Schratzberger, Daniel Himmelbauer, Wolfgang Eder, Michael Weiser, Berthold Stöger, Karl Kirchner

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引用次数: 0

摘要

用ipso取代的P（C-X）PY配体（X）处理[Co2（CO）8] = Br、Cl；R = iPr，tBu）轴承Y = NH和CH2连接体在溶剂热条件下得到五配位的Co（I）和Co（III）配合物[CoI（PCPY-R）（Co）2]和[CoIII（PCPY-R）X2]。后者是顺磁性的，表现出3.0-3.3μB的溶液磁矩，这与对应于两个不成对电子的d6中间自旋系统一致。在P（C-X）PY配体（X = Br、Cl；R = tBu；Y = NH）形成正方形平面Co（II）配合物[Co（PCPNH-tBu）X]是有利的。该配合物产生1.8μB的磁矩，这与对应于一个未配对电子的d7低自旋系统一致。所有的配合物都通过光谱技术（NMR、IR）、HR-MS进行了表征。具有代表性的配合物也通过X射线晶体学进行了表征。图形摘要：补充信息：在线版本包含补充材料，可访问10.1007/s00706-023-03123-x。

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Solvothermal synthesis of cobalt PCP pincer complexes from [Co₂(CO)₈].

Treatment of [Co₂(CO)₈] with the ipso-substituted P(C-X)P^Y ligands (X = Br, Cl; R = iPr, tBu) bearing Y = NH and CH₂ linkers under solvothermal conditions affords the five-coordinate Co(I) and Co(III) complexes [Co^I(PCP^Y-R)(CO)₂] and [Co^III(PCP^Y-R)X₂]. The later are paramagnetic exhibiting a solution magnetic moment in the range of 3.0-3.3 μ_B which is consistent with a d⁶ intermediate spin system corresponding to two unpaired electrons. In the case of P(C-X)P^Y ligands (X = Br, Cl; R = tBu; Y = NH) the formation of the square planar Co(II) complex [Co(PCP^NH-tBu)X] was favored. This complex gives rise to a magnetic moment of 1.8 μ_B being consistent with a d⁷ low spin system corresponding to one unpaired electron. All complexes are characterized by means of spectroscopic techniques (NMR, IR), HR-MS. Representative complexes were also characterized by X-ray crystallography.

Graphical abstract:

Supplementary information: The online version contains supplementary material available at 10.1007/s00706-023-03123-x.

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来源期刊

Monatshefte Fur Chemie 化学-化学综合

CiteScore

3.70

自引率

5.60%

发文量

116

审稿时长

3.3 months

期刊介绍： "Monatshefte für Chemie/Chemical Monthly" was originally conceived as an Austrian journal of chemistry. It has evolved into an international journal covering all branches of chemistry. Featuring the most recent advances in research in analytical chemistry, biochemistry, inorganic, medicinal, organic, physical, structural, and theoretical chemistry, Chemical Monthly publishes refereed original papers and a section entitled "Short Communications". Reviews, symposia in print, and issues devoted to special fields will also be considered.