{"title":"基于吡咯的第 4 组 PNP 钳子复合物的合成与表征","authors":"Gerald Tomsu, Berthold Stöger, Karl Kirchner","doi":"10.1007/s00706-024-03171-x","DOIUrl":null,"url":null,"abstract":"<p>The synthesis, characterization, and reactivity of several group 4 metal complexes featuring a central anionic pyrrole moiety connected via CH<sub>2</sub> linkers to two phosphine donors is described. Treatment of [P(NH)P-<i>i</i>Pr] with [MCl<sub>4</sub>(THF)<sub>2</sub>] (M = Zr, Hf) in the presence of base yields the dimeric complexes [M(PNP<sup><i>i</i>Pr</sup>)(μ-Cl)(Cl)<sub>2</sub>]<sub>2</sub> featuring two bridging chloride ligands. These complexes react with sodium cyclopentadienyl and SiMe<sub>3</sub>I to give the mononuclear complexes [M(PNP<sup><i>i</i>Pr</sup>)(η<sup>5</sup>-Cp)(Cl)<sub>2</sub>] and [M(PNP<sup><i>i</i>Pr</sup>)(I)<sub>3</sub>], respectively. The latter react with MeMgBr to form the trialkyl complexes [M(PNP<sup><i>i</i>Pr</sup>)(Me)<sub>3</sub>]. Upon treatment of [Ti(NMe<sub>2</sub>)<sub>4</sub>] with [P(NH)P-<i>i</i>Pr] a complex with the general formula [Ti(PNP<sup><i>i</i>Pr</sup>)(NMe<sub>2</sub>)<sub>3</sub>] is obtained. DFT calculations revealed that the most stable species is [Ti(κ<sup>1</sup><i>N</i>- PNP<sup><i>i</i>Pr</sup>)(NMe<sub>2</sub>)<sub>3</sub>] featuring a κ<sup>1</sup><i>N</i>-bound PNP ligand. When [P(NH)P-<i>i</i>Pr] is reacted with [Ti(NMe<sub>2</sub>)<sub>4</sub>] in CH<sub>2</sub>Cl<sub>2</sub> complex [Ti(PNP<sup><i>i</i>Pr</sup>)(Cl)<sub>2</sub>(NMe<sub>2</sub>)] is formed. Treatment of a solution of [P(NH)P-<i>i</i>Pr] and [Zr(NMe<sub>2</sub>)<sub>4</sub>] with SiMe<sub>3</sub>Br affords the anionic seven-coordinate tetrabromo complex [Zr(PNP<sup><i>i</i>Pr</sup>)(Br)<sub>4</sub>][H<sub>2</sub>NMe<sub>2</sub>]. The corresponding hafnium complex [Hf(PNP<sup><i>i</i>Pr</sup>)(Br)<sub>4</sub>][H<sub>2</sub>NEt<sub>2</sub>] is obtained in similar fashion by utilizing [Hf(NEt<sub>2</sub>)<sub>4</sub>] as metal precursor. All complexes are characterized by means of NMR spectroscopy. Representative complexes were also characterized by X-ray crystallography.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>\n","PeriodicalId":19011,"journal":{"name":"Monatshefte für Chemie / Chemical Monthly","volume":"20 1","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2024-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis and characterization of pyrrole-based group 4 PNP pincer complexes\",\"authors\":\"Gerald Tomsu, Berthold Stöger, Karl Kirchner\",\"doi\":\"10.1007/s00706-024-03171-x\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The synthesis, characterization, and reactivity of several group 4 metal complexes featuring a central anionic pyrrole moiety connected via CH<sub>2</sub> linkers to two phosphine donors is described. Treatment of [P(NH)P-<i>i</i>Pr] with [MCl<sub>4</sub>(THF)<sub>2</sub>] (M = Zr, Hf) in the presence of base yields the dimeric complexes [M(PNP<sup><i>i</i>Pr</sup>)(μ-Cl)(Cl)<sub>2</sub>]<sub>2</sub> featuring two bridging chloride ligands. These complexes react with sodium cyclopentadienyl and SiMe<sub>3</sub>I to give the mononuclear complexes [M(PNP<sup><i>i</i>Pr</sup>)(η<sup>5</sup>-Cp)(Cl)<sub>2</sub>] and [M(PNP<sup><i>i</i>Pr</sup>)(I)<sub>3</sub>], respectively. The latter react with MeMgBr to form the trialkyl complexes [M(PNP<sup><i>i</i>Pr</sup>)(Me)<sub>3</sub>]. Upon treatment of [Ti(NMe<sub>2</sub>)<sub>4</sub>] with [P(NH)P-<i>i</i>Pr] a complex with the general formula [Ti(PNP<sup><i>i</i>Pr</sup>)(NMe<sub>2</sub>)<sub>3</sub>] is obtained. DFT calculations revealed that the most stable species is [Ti(κ<sup>1</sup><i>N</i>- PNP<sup><i>i</i>Pr</sup>)(NMe<sub>2</sub>)<sub>3</sub>] featuring a κ<sup>1</sup><i>N</i>-bound PNP ligand. When [P(NH)P-<i>i</i>Pr] is reacted with [Ti(NMe<sub>2</sub>)<sub>4</sub>] in CH<sub>2</sub>Cl<sub>2</sub> complex [Ti(PNP<sup><i>i</i>Pr</sup>)(Cl)<sub>2</sub>(NMe<sub>2</sub>)] is formed. Treatment of a solution of [P(NH)P-<i>i</i>Pr] and [Zr(NMe<sub>2</sub>)<sub>4</sub>] with SiMe<sub>3</sub>Br affords the anionic seven-coordinate tetrabromo complex [Zr(PNP<sup><i>i</i>Pr</sup>)(Br)<sub>4</sub>][H<sub>2</sub>NMe<sub>2</sub>]. The corresponding hafnium complex [Hf(PNP<sup><i>i</i>Pr</sup>)(Br)<sub>4</sub>][H<sub>2</sub>NEt<sub>2</sub>] is obtained in similar fashion by utilizing [Hf(NEt<sub>2</sub>)<sub>4</sub>] as metal precursor. All complexes are characterized by means of NMR spectroscopy. Representative complexes were also characterized by X-ray crystallography.</p><h3 data-test=\\\"abstract-sub-heading\\\">Graphical abstract</h3>\\n\",\"PeriodicalId\":19011,\"journal\":{\"name\":\"Monatshefte für Chemie / Chemical Monthly\",\"volume\":\"20 1\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-02-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Monatshefte für Chemie / Chemical Monthly\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1007/s00706-024-03171-x\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Monatshefte für Chemie / Chemical Monthly","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1007/s00706-024-03171-x","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Synthesis and characterization of pyrrole-based group 4 PNP pincer complexes
The synthesis, characterization, and reactivity of several group 4 metal complexes featuring a central anionic pyrrole moiety connected via CH2 linkers to two phosphine donors is described. Treatment of [P(NH)P-iPr] with [MCl4(THF)2] (M = Zr, Hf) in the presence of base yields the dimeric complexes [M(PNPiPr)(μ-Cl)(Cl)2]2 featuring two bridging chloride ligands. These complexes react with sodium cyclopentadienyl and SiMe3I to give the mononuclear complexes [M(PNPiPr)(η5-Cp)(Cl)2] and [M(PNPiPr)(I)3], respectively. The latter react with MeMgBr to form the trialkyl complexes [M(PNPiPr)(Me)3]. Upon treatment of [Ti(NMe2)4] with [P(NH)P-iPr] a complex with the general formula [Ti(PNPiPr)(NMe2)3] is obtained. DFT calculations revealed that the most stable species is [Ti(κ1N- PNPiPr)(NMe2)3] featuring a κ1N-bound PNP ligand. When [P(NH)P-iPr] is reacted with [Ti(NMe2)4] in CH2Cl2 complex [Ti(PNPiPr)(Cl)2(NMe2)] is formed. Treatment of a solution of [P(NH)P-iPr] and [Zr(NMe2)4] with SiMe3Br affords the anionic seven-coordinate tetrabromo complex [Zr(PNPiPr)(Br)4][H2NMe2]. The corresponding hafnium complex [Hf(PNPiPr)(Br)4][H2NEt2] is obtained in similar fashion by utilizing [Hf(NEt2)4] as metal precursor. All complexes are characterized by means of NMR spectroscopy. Representative complexes were also characterized by X-ray crystallography.
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