锰二甲基氢化配合物：与二氧化碳、二苯甲酮和二异丙基碳二亚胺的反应性

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-09-18 DOI:10.1039/d5dt01701g

Jeffrey S. Price, David J. H. Emslie

{"title":"锰二甲基氢化配合物：与二氧化碳、二苯甲酮和二异丙基碳二亚胺的反应性","authors":"Jeffrey S. Price, David J. H. Emslie","doi":"10.1039/d5dt01701g","DOIUrl":null,"url":null,"abstract":"Reactions of bis(hydrocarbyl)germylene manganese(I) hydride complexes [(dmpe)2MnH(<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>GeR2)] (1a: R = Ph, 1b: R = Et) with carbon dioxide yielded the previously reported carbonyl formate complex [(dmpe)2Mn(κ1-O2CH)(CO)] (3) via the unstable κ2-formatogermyl intermediates [(dmpe)2Mn{κ2-GeR2(OCHO)}] (5a: R = Ph, 5b: R = Et). By contrast, addition of CO2 to [(dmpe)2MnH(<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>GenBuH)] (2a), which contains a terminal GeH substitutent, resulted in the sequential formation of (i) the formatogermylene hydride complex [(dmpe)2MnH{<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>GenBu(κ1-O2CH)}] (6), (ii) the isolable metallacyclic κ2-formatogermyl complex [(dmpe)2Mn{κ2-GenBu(κ1-O2CH)(OCHO)}] (7), and with heating(III) complex 3. Exposure of 2a to benzophenone also afforded a new germylene hydride complex, [(dmpe)2MnH{<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>GenBu(OCHPh2)}] (8). Reactions of 1a–b and 2a with C(NiPr)2 afforded a family of stable metallacyclic κ2-amidinylgermyl complexes [(dmpe)2Mn{κ2-GeRR′(NiPrCHNiPr)}] (9a: R = R′ = Ph, 9b: R = R′ = Et, 10: R = nBu and R′ = H). Addition of carbon dioxide to 10 yielded [(dmpe)2Mn{κ2-GenBu(κ1-O2CH)(NiPrCHNiPr)}] (11), and reaction of CO2 with the κ2-amidinylsilyl derivative [(dmpe)2Mn{κ2-SiPhH(NiPrCHNiPr)}] afforded [(dmpe)2Mn{κ2-SiPh(κ1-O2CH)(NiPrCHNiPr)}] (12). Complexes 6, 7, 8, 9a, 11, and 12 were crystallographically characterized, and DFT calculations were conducted to probe the effect that different substituents on Ge have on Mn–Ge bonding in κ2-formatogermyl, κ2-amidinylgermyl, and germylene complexes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"89 1","pages":""},"PeriodicalIF":3.3000,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Manganese germylene hydride complexes: reactivity with carbon dioxide, benzophenone, and diisopropylcarbodiimide\",\"authors\":\"Jeffrey S. Price, David J. H. Emslie\",\"doi\":\"10.1039/d5dt01701g\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Reactions of bis(hydrocarbyl)germylene manganese(I) hydride complexes [(dmpe)2MnH(<img alt=\\\"[double bond, length as m-dash]\\\" border=\\\"0\\\" src=\\\"https://www.rsc.org/images/entities/char_e001.gif\\\"/>GeR2)] (1a: R = Ph, 1b: R = Et) with carbon dioxide yielded the previously reported carbonyl formate complex [(dmpe)2Mn(κ1-O2CH)(CO)] (3) via the unstable κ2-formatogermyl intermediates [(dmpe)2Mn{κ2-GeR2(OCHO)}] (5a: R = Ph, 5b: R = Et). By contrast, addition of CO2 to [(dmpe)2MnH(<img alt=\\\"[double bond, length as m-dash]\\\" border=\\\"0\\\" src=\\\"https://www.rsc.org/images/entities/char_e001.gif\\\"/>GenBuH)] (2a), which contains a terminal GeH substitutent, resulted in the sequential formation of (i) the formatogermylene hydride complex [(dmpe)2MnH{<img alt=\\\"[double bond, length as m-dash]\\\" border=\\\"0\\\" src=\\\"https://www.rsc.org/images/entities/char_e001.gif\\\"/>GenBu(κ1-O2CH)}] (6), (ii) the isolable metallacyclic κ2-formatogermyl complex [(dmpe)2Mn{κ2-GenBu(κ1-O2CH)(OCHO)}] (7), and with heating(III) complex 3. Exposure of 2a to benzophenone also afforded a new germylene hydride complex, [(dmpe)2MnH{<img alt=\\\"[double bond, length as m-dash]\\\" border=\\\"0\\\" src=\\\"https://www.rsc.org/images/entities/char_e001.gif\\\"/>GenBu(OCHPh2)}] (8). Reactions of 1a–b and 2a with C(NiPr)2 afforded a family of stable metallacyclic κ2-amidinylgermyl complexes [(dmpe)2Mn{κ2-GeRR′(NiPrCHNiPr)}] (9a: R = R′ = Ph, 9b: R = R′ = Et, 10: R = nBu and R′ = H). Addition of carbon dioxide to 10 yielded [(dmpe)2Mn{κ2-GenBu(κ1-O2CH)(NiPrCHNiPr)}] (11), and reaction of CO2 with the κ2-amidinylsilyl derivative [(dmpe)2Mn{κ2-SiPhH(NiPrCHNiPr)}] afforded [(dmpe)2Mn{κ2-SiPh(κ1-O2CH)(NiPrCHNiPr)}] (12). Complexes 6, 7, 8, 9a, 11, and 12 were crystallographically characterized, and DFT calculations were conducted to probe the effect that different substituents on Ge have on Mn–Ge bonding in κ2-formatogermyl, κ2-amidinylgermyl, and germylene complexes.\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\"89 1\",\"pages\":\"\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-09-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d5dt01701g\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5dt01701g","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

摘要

双（hydrocaryl）germylene锰(I)氢化物配合物[(dmpe)2MnH(GeR2)] （1a: R = Ph, 1b: R = Et）与二氧化碳反应，通过不稳定的κ2- formatogmyl中间体[(dmpe)2Mn{κ2-GeR2(OCHO)}] （5a: R = Ph, 5b: R = Et）生成甲酸羰基配合物[(dmpe)2Mn(κ1-O2CH)(CO)](3)。与此相反，在含有末端GeH取代基的[(dmpe)2MnH(GenBuH)] （2a）中加入CO2后，依次生成(i)正丁二烯氢化物配合物[(dmpe)2MnH{GenBu(κ1-O2CH)}] (6), （ii）可分离的金属环κ2-正丁二烯配合物[(dmpe)2Mn{κ2-GenBu(κ1-O2CH)(OCHO)}](7)和加热（III）配合物3。暴露于二苯甲酮的2a也产生了新的二甲苯氢化物配合物[(dmpe)2MnH{GenBu(OCHPh2)}](8)。1a-b和2a与C(NiPr)2反应形成了稳定的金属环κ2-氨基基germyl配合物家族[(dmpe)2Mn{κ2-GeRR ' (NiPrCHNiPr)}] （9a: R = R ' = Ph, 9b: R = R ' = Et, 10: R = nBu和R ' = H）。10加入二氧化碳得到[(dmpe)2Mn{κ2-GenBu(κ1-O2CH)(NiPrCHNiPr)}](11)，与κ2-氨基基硅基衍生物[(dmpe)2Mn{κ2-SiPhH(NiPrCHNiPr)}]反应得到[(dmpe)2Mn{κ2-SiPh(κ1-O2CH)(NiPrCHNiPr)}]（12）。对配合物6、7、8、9a、11和12进行了晶体学表征，并通过DFT计算探讨了不同取代基对κ2- formatgermyl、κ2-amidinylgermyl和germylene配合物中Mn-Ge键的影响。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Manganese germylene hydride complexes: reactivity with carbon dioxide, benzophenone, and diisopropylcarbodiimide

查看原文本刊更多论文

Manganese germylene hydride complexes: reactivity with carbon dioxide, benzophenone, and diisopropylcarbodiimide

Reactions of bis(hydrocarbyl)germylene manganese(I) hydride complexes [(dmpe)₂MnH( [double bond, length as m-dash]

GeR₂)] (1a: R = Ph, 1b: R = Et) with carbon dioxide yielded the previously reported carbonyl formate complex [(dmpe)₂Mn(κ¹-O₂CH)(CO)] (3) via the unstable κ²-formatogermyl intermediates [(dmpe)₂Mn{κ²-GeR₂(OCHO)}] (5a: R = Ph, 5b: R = Et). By contrast, addition of CO₂ to [(dmpe)₂MnH( [double bond, length as m-dash]

GeⁿBuH)] (2a), which contains a terminal GeH substitutent, resulted in the sequential formation of (i) the formatogermylene hydride complex [(dmpe)₂MnH{ [double bond, length as m-dash]

GeⁿBu(κ¹-O₂CH)}] (6), (ii) the isolable metallacyclic κ²-formatogermyl complex [(dmpe)₂Mn{κ²-GeⁿBu(κ¹-O₂CH)(OCHO)}] (7), and with heating(III) complex 3. Exposure of 2a to benzophenone also afforded a new germylene hydride complex, [(dmpe)₂MnH{ [double bond, length as m-dash]

GeⁿBu(OCHPh₂)}] (8). Reactions of 1a–b and 2a with C(NⁱPr)₂ afforded a family of stable metallacyclic κ²-amidinylgermyl complexes [(dmpe)₂Mn{κ²-GeRR′(NⁱPrCHNⁱPr)}] (9a: R = R′ = Ph, 9b: R = R′ = Et, 10: R = ⁿBu and R′ = H). Addition of carbon dioxide to 10 yielded [(dmpe)₂Mn{κ²-GeⁿBu(κ¹-O₂CH)(NⁱPrCHNⁱPr)}] (11), and reaction of CO₂ with the κ²-amidinylsilyl derivative [(dmpe)₂Mn{κ²-SiPhH(NⁱPrCHNⁱPr)}] afforded [(dmpe)₂Mn{κ²-SiPh(κ¹-O₂CH)(NⁱPrCHNⁱPr)}] (12). Complexes 6, 7, 8, 9a, 11, and 12 were crystallographically characterized, and DFT calculations were conducted to probe the effect that different substituents on Ge have on Mn–Ge bonding in κ²-formatogermyl, κ²-amidinylgermyl, and germylene complexes.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.