Heiko Schratzberger, Daniel Himmelbauer, Wolfgang Eder, Michael Weiser, Berthold Stöger, Karl Kirchner
{"title":"由[Co2（CO）8]溶剂热合成钴-五氯苯酚钳形配合物。","authors":"Heiko Schratzberger, Daniel Himmelbauer, Wolfgang Eder, Michael Weiser, Berthold Stöger, Karl Kirchner","doi":"10.1007/s00706-023-03123-x","DOIUrl":null,"url":null,"abstract":"<p><p>Treatment of [Co<sub>2</sub>(CO)<sub>8</sub>] with the <i>ipso</i>-substituted P(C-X)P<sup>Y</sup> ligands (X = Br, Cl; R = <i>i</i>Pr, <i>t</i>Bu) bearing Y = NH and CH<sub>2</sub> linkers under solvothermal conditions affords the five-coordinate Co(I) and Co(III) complexes [Co<sup>I</sup>(PCP<sup>Y</sup>-R)(CO)<sub>2</sub>] and [Co<sup>III</sup>(PCP<sup>Y</sup>-R)X<sub>2</sub>]. The later are paramagnetic exhibiting a solution magnetic moment in the range of 3.0-3.3 μ<sub>B</sub> which is consistent with a d<sup>6</sup> intermediate spin system corresponding to two unpaired electrons. In the case of P(C-X)P<sup>Y</sup> ligands (X = Br, Cl; R = <i>t</i>Bu; Y = NH) the formation of the square planar Co(II) complex [Co(PCP<sup>NH</sup>-<i>t</i>Bu)X] was favored. This complex gives rise to a magnetic moment of 1.8 μ<sub>B</sub> being consistent with a d<sup>7</sup> 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.</p><p><strong>Graphical abstract: </strong></p><p><strong>Supplementary information: </strong>The online version contains supplementary material available at 10.1007/s00706-023-03123-x.</p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":null,"pages":null},"PeriodicalIF":1.7000,"publicationDate":"2023-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10620272/pdf/","citationCount":"0","resultStr":"{\"title\":\"Solvothermal synthesis of cobalt PCP pincer complexes from [Co<sub>2</sub>(CO)<sub>8</sub>].\",\"authors\":\"Heiko Schratzberger, Daniel Himmelbauer, Wolfgang Eder, Michael Weiser, Berthold Stöger, Karl Kirchner\",\"doi\":\"10.1007/s00706-023-03123-x\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Treatment of [Co<sub>2</sub>(CO)<sub>8</sub>] with the <i>ipso</i>-substituted P(C-X)P<sup>Y</sup> ligands (X = Br, Cl; R = <i>i</i>Pr, <i>t</i>Bu) bearing Y = NH and CH<sub>2</sub> linkers under solvothermal conditions affords the five-coordinate Co(I) and Co(III) complexes [Co<sup>I</sup>(PCP<sup>Y</sup>-R)(CO)<sub>2</sub>] and [Co<sup>III</sup>(PCP<sup>Y</sup>-R)X<sub>2</sub>]. The later are paramagnetic exhibiting a solution magnetic moment in the range of 3.0-3.3 μ<sub>B</sub> which is consistent with a d<sup>6</sup> intermediate spin system corresponding to two unpaired electrons. In the case of P(C-X)P<sup>Y</sup> ligands (X = Br, Cl; R = <i>t</i>Bu; Y = NH) the formation of the square planar Co(II) complex [Co(PCP<sup>NH</sup>-<i>t</i>Bu)X] was favored. This complex gives rise to a magnetic moment of 1.8 μ<sub>B</sub> being consistent with a d<sup>7</sup> 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.</p><p><strong>Graphical abstract: </strong></p><p><strong>Supplementary information: </strong>The online version contains supplementary material available at 10.1007/s00706-023-03123-x.</p>\",\"PeriodicalId\":18766,\"journal\":{\"name\":\"Monatshefte Fur Chemie\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.7000,\"publicationDate\":\"2023-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10620272/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Monatshefte Fur Chemie\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1007/s00706-023-03123-x\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2023/9/9 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Monatshefte Fur Chemie","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1007/s00706-023-03123-x","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2023/9/9 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Solvothermal synthesis of cobalt PCP pincer complexes from [Co2(CO)8].
Treatment of [Co2(CO)8] with the ipso-substituted P(C-X)PY 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 [CoI(PCPY-R)(CO)2] and [CoIII(PCPY-R)X2]. The later are paramagnetic exhibiting a solution magnetic moment in the range of 3.0-3.3 μB which is consistent with a d6 intermediate spin system corresponding to two unpaired electrons. In the case of P(C-X)PY ligands (X = Br, Cl; R = tBu; Y = NH) the formation of the square planar Co(II) complex [Co(PCPNH-tBu)X] was favored. This complex gives rise to a magnetic moment of 1.8 μB 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.
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.
![Solvothermal synthesis of cobalt PCP pincer complexes from [Co<sub>2</sub>(CO)<sub>8</sub>].](https://img.booksci.cn/booksciimg/2023-1/2023120478251433521392962611472.jpg)
![Solvothermal synthesis of cobalt PCP pincer complexes from [Co<sub>2</sub>(CO)<sub>8</sub>].](https://img.booksci.cn/booksciimg/2023-1/2023120478294157398866356831678.jpg)
![Solvothermal synthesis of cobalt PCP pincer complexes from [Co<sub>2</sub>(CO)<sub>8</sub>].](https://img.booksci.cn/booksciimg/2023-1/2023120478299634947837645026548.jpg)
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