Mathias Glatz, Jan Pecak, Lena Haager, Berthold Stoeger, Karl Kirchner
{"title":"双和三羰基Mn（I）和Re（I）PNP钳形配合物的合成与表征。","authors":"Mathias Glatz, Jan Pecak, Lena Haager, Berthold Stoeger, Karl Kirchner","doi":"10.1007/s00706-018-2307-7","DOIUrl":null,"url":null,"abstract":"<p><strong>Abstract: </strong>A series of neutral bis- and cationic tris-carbonyl complexes of the types <i>cis</i>-[M(κ<sup>3</sup> <i>P,N,P</i>-PNP)(CO)<sub>2</sub>Y] and [M(κ<sup>3</sup> <i>P,N,P</i>-PNP)(CO)<sub>3</sub>]<sup>+</sup> was prepared by reacting [M(CO)<sub>5</sub>Y] (M = Mn, Re; Y = Cl or Br) with PNP pincer ligands derived from the 2,6-diaminopyridine, 2,6-dihydroxypyridine, and 2,6-lutidine scaffolds. With the most bulky ligand PNP<sup>NH</sup>-<i>t</i>Bu, the cationic square-pyramidal 16e bis-carbonyl complex [Mn(PNP<sup>NH</sup>-<i>t</i>Bu)(CO)<sub>2</sub>]<sup>+</sup> was obtained. In contrast, in the case of rhenium, the 18e complex [Re(PNP<sup>NH</sup>-<i>t</i>Bu)(CO)<sub>3</sub>]<sup>+</sup> was formed. The dissociation of CO was studied by means of DFT calculation revealing in agreement with experimental findings that CO release from [M(κ<sup>3</sup> <i>P,N,P</i>-PNP)(CO)<sub>3</sub>]<sup>+</sup> is in general endergonic, while for [Mn(κ<sup>3</sup> <i>P,N,P</i>-PNP<sup>NH</sup>-<i>t</i>Bu)(CO)<sub>3</sub>]<sup>+</sup>, this process is thermodynamically favored. X-ray structures of representative complexes are provided.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"150 1","pages":"111-119"},"PeriodicalIF":1.7000,"publicationDate":"2019-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6320747/pdf/","citationCount":"0","resultStr":"{\"title\":\"Synthesis and characterization of bis- and tris-carbonyl Mn(I) and Re(I) PNP pincer complexes.\",\"authors\":\"Mathias Glatz, Jan Pecak, Lena Haager, Berthold Stoeger, Karl Kirchner\",\"doi\":\"10.1007/s00706-018-2307-7\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><strong>Abstract: </strong>A series of neutral bis- and cationic tris-carbonyl complexes of the types <i>cis</i>-[M(κ<sup>3</sup> <i>P,N,P</i>-PNP)(CO)<sub>2</sub>Y] and [M(κ<sup>3</sup> <i>P,N,P</i>-PNP)(CO)<sub>3</sub>]<sup>+</sup> was prepared by reacting [M(CO)<sub>5</sub>Y] (M = Mn, Re; Y = Cl or Br) with PNP pincer ligands derived from the 2,6-diaminopyridine, 2,6-dihydroxypyridine, and 2,6-lutidine scaffolds. With the most bulky ligand PNP<sup>NH</sup>-<i>t</i>Bu, the cationic square-pyramidal 16e bis-carbonyl complex [Mn(PNP<sup>NH</sup>-<i>t</i>Bu)(CO)<sub>2</sub>]<sup>+</sup> was obtained. In contrast, in the case of rhenium, the 18e complex [Re(PNP<sup>NH</sup>-<i>t</i>Bu)(CO)<sub>3</sub>]<sup>+</sup> was formed. The dissociation of CO was studied by means of DFT calculation revealing in agreement with experimental findings that CO release from [M(κ<sup>3</sup> <i>P,N,P</i>-PNP)(CO)<sub>3</sub>]<sup>+</sup> is in general endergonic, while for [Mn(κ<sup>3</sup> <i>P,N,P</i>-PNP<sup>NH</sup>-<i>t</i>Bu)(CO)<sub>3</sub>]<sup>+</sup>, this process is thermodynamically favored. X-ray structures of representative complexes are provided.</p><p><strong>Graphical abstract: </strong></p>\",\"PeriodicalId\":18766,\"journal\":{\"name\":\"Monatshefte Fur Chemie\",\"volume\":\"150 1\",\"pages\":\"111-119\"},\"PeriodicalIF\":1.7000,\"publicationDate\":\"2019-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6320747/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Monatshefte Fur Chemie\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1007/s00706-018-2307-7\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2018/10/20 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/s00706-018-2307-7","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2018/10/20 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Synthesis and characterization of bis- and tris-carbonyl Mn(I) and Re(I) PNP pincer complexes.
Abstract: A series of neutral bis- and cationic tris-carbonyl complexes of the types cis-[M(κ3P,N,P-PNP)(CO)2Y] and [M(κ3P,N,P-PNP)(CO)3]+ was prepared by reacting [M(CO)5Y] (M = Mn, Re; Y = Cl or Br) with PNP pincer ligands derived from the 2,6-diaminopyridine, 2,6-dihydroxypyridine, and 2,6-lutidine scaffolds. With the most bulky ligand PNPNH-tBu, the cationic square-pyramidal 16e bis-carbonyl complex [Mn(PNPNH-tBu)(CO)2]+ was obtained. In contrast, in the case of rhenium, the 18e complex [Re(PNPNH-tBu)(CO)3]+ was formed. The dissociation of CO was studied by means of DFT calculation revealing in agreement with experimental findings that CO release from [M(κ3P,N,P-PNP)(CO)3]+ is in general endergonic, while for [Mn(κ3P,N,P-PNPNH-tBu)(CO)3]+, this process is thermodynamically favored. X-ray structures of representative complexes are provided.
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.
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