{"title":"强效双(膦)-1,8-萘啶配体的双铜μ-硼烷基络合物介导的 CO2 和 CS2 二硼烷还原反应","authors":"Matthew S. See, Pablo Ríos and T. Don Tilley*, ","doi":"10.1021/acs.organomet.4c00122","DOIUrl":null,"url":null,"abstract":"<p >A dinucleating 1,8-naphthyridine ligand featuring fluorene-9,9-diyl-linked phosphino side arms (PNNP<sup>Flu</sup>) was synthesized and used to obtain the cationic dicopper complexes <b>2</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-Ph)][NTf<sub>2</sub>]; [NTf<sub>2</sub>] = bis(trifluoromethane)sulfonimide, <b>6</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-CCPh)][NTf<sub>2</sub>], and <b>3</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-O<sup><i>t</i></sup>Bu)][NTf<sub>2</sub>]. Complex <b>3</b> reacted with diboranes to afford dicopper μ-boryl species (<b>4</b>, with μ-Bcat; cat = catecholate and <b>5</b>, with μ-Bpin; pin = pinacolate) that are more reactive in C(sp)–H bond activations and toward activations of CO<sub>2</sub> and CS<sub>2</sub>, compared to dicopper μ-boryl complexes supported by a 1,8-naphthyridine-based ligand with di(pyridyl) side arms. The solid-state structures and DFT analysis indicate that the higher reactivities of <b>4</b> and <b>5</b> relate to changes in the coordination sphere of copper, rather than to perturbations on the Cu–B bonding interactions. Addition of xylyl isocyanide (CNXyl) to <b>4</b> gave <b>7</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-Bcat)(CNXyl)][NTf<sub>2</sub>], demonstrating that the lower coordination number at copper is chemically significant. Reactions of <b>4</b> and <b>5</b> with CO<sub>2</sub> yielded the corresponding dicopper borate complexes (<b>8</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-OBcat)][NTf<sub>2</sub>]; <b>9</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-OBpin)][NTf<sub>2</sub>]), with <b>4</b> demonstrating catalytic reduction in the presence of excess diborane. Related reactions of <b>4</b> and <b>5</b> with CS<sub>2</sub> provided insertion products <b>10</b>, {[(PNNP<sup>Flu</sup>)Cu<sub>2</sub>]<sub>2</sub>[μ-S<sub>2</sub>C(Bcat)<sub>2</sub>]}[NTf<sub>2</sub>]<sub>2</sub>, and <b>11</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ,κ<sup>2</sup>-S<sub>2</sub>CBpin)][NTf<sub>2</sub>], respectively. These products feature Cu–S–C–B linkages analogous to those of proposed CO<sub>2</sub> insertion intermediate.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00122","citationCount":"0","resultStr":"{\"title\":\"Diborane Reductions of CO2 and CS2 Mediated by Dicopper μ-Boryl Complexes of a Robust Bis(phosphino)-1,8-naphthyridine Ligand\",\"authors\":\"Matthew S. See, Pablo Ríos and T. Don Tilley*, \",\"doi\":\"10.1021/acs.organomet.4c00122\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A dinucleating 1,8-naphthyridine ligand featuring fluorene-9,9-diyl-linked phosphino side arms (PNNP<sup>Flu</sup>) was synthesized and used to obtain the cationic dicopper complexes <b>2</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-Ph)][NTf<sub>2</sub>]; [NTf<sub>2</sub>] = bis(trifluoromethane)sulfonimide, <b>6</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-CCPh)][NTf<sub>2</sub>], and <b>3</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-O<sup><i>t</i></sup>Bu)][NTf<sub>2</sub>]. Complex <b>3</b> reacted with diboranes to afford dicopper μ-boryl species (<b>4</b>, with μ-Bcat; cat = catecholate and <b>5</b>, with μ-Bpin; pin = pinacolate) that are more reactive in C(sp)–H bond activations and toward activations of CO<sub>2</sub> and CS<sub>2</sub>, compared to dicopper μ-boryl complexes supported by a 1,8-naphthyridine-based ligand with di(pyridyl) side arms. The solid-state structures and DFT analysis indicate that the higher reactivities of <b>4</b> and <b>5</b> relate to changes in the coordination sphere of copper, rather than to perturbations on the Cu–B bonding interactions. Addition of xylyl isocyanide (CNXyl) to <b>4</b> gave <b>7</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-Bcat)(CNXyl)][NTf<sub>2</sub>], demonstrating that the lower coordination number at copper is chemically significant. Reactions of <b>4</b> and <b>5</b> with CO<sub>2</sub> yielded the corresponding dicopper borate complexes (<b>8</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-OBcat)][NTf<sub>2</sub>]; <b>9</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ-OBpin)][NTf<sub>2</sub>]), with <b>4</b> demonstrating catalytic reduction in the presence of excess diborane. Related reactions of <b>4</b> and <b>5</b> with CS<sub>2</sub> provided insertion products <b>10</b>, {[(PNNP<sup>Flu</sup>)Cu<sub>2</sub>]<sub>2</sub>[μ-S<sub>2</sub>C(Bcat)<sub>2</sub>]}[NTf<sub>2</sub>]<sub>2</sub>, and <b>11</b>, [(PNNP<sup>Flu</sup>)Cu<sub>2</sub>(μ,κ<sup>2</sup>-S<sub>2</sub>CBpin)][NTf<sub>2</sub>], respectively. These products feature Cu–S–C–B linkages analogous to those of proposed CO<sub>2</sub> insertion intermediate.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-05-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.organomet.4c00122\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00122\",\"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":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00122","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Diborane Reductions of CO2 and CS2 Mediated by Dicopper μ-Boryl Complexes of a Robust Bis(phosphino)-1,8-naphthyridine Ligand
A dinucleating 1,8-naphthyridine ligand featuring fluorene-9,9-diyl-linked phosphino side arms (PNNPFlu) was synthesized and used to obtain the cationic dicopper complexes 2, [(PNNPFlu)Cu2(μ-Ph)][NTf2]; [NTf2] = bis(trifluoromethane)sulfonimide, 6, [(PNNPFlu)Cu2(μ-CCPh)][NTf2], and 3, [(PNNPFlu)Cu2(μ-OtBu)][NTf2]. Complex 3 reacted with diboranes to afford dicopper μ-boryl species (4, with μ-Bcat; cat = catecholate and 5, with μ-Bpin; pin = pinacolate) that are more reactive in C(sp)–H bond activations and toward activations of CO2 and CS2, compared to dicopper μ-boryl complexes supported by a 1,8-naphthyridine-based ligand with di(pyridyl) side arms. The solid-state structures and DFT analysis indicate that the higher reactivities of 4 and 5 relate to changes in the coordination sphere of copper, rather than to perturbations on the Cu–B bonding interactions. Addition of xylyl isocyanide (CNXyl) to 4 gave 7, [(PNNPFlu)Cu2(μ-Bcat)(CNXyl)][NTf2], demonstrating that the lower coordination number at copper is chemically significant. Reactions of 4 and 5 with CO2 yielded the corresponding dicopper borate complexes (8, [(PNNPFlu)Cu2(μ-OBcat)][NTf2]; 9, [(PNNPFlu)Cu2(μ-OBpin)][NTf2]), with 4 demonstrating catalytic reduction in the presence of excess diborane. Related reactions of 4 and 5 with CS2 provided insertion products 10, {[(PNNPFlu)Cu2]2[μ-S2C(Bcat)2]}[NTf2]2, and 11, [(PNNPFlu)Cu2(μ,κ2-S2CBpin)][NTf2], respectively. These products feature Cu–S–C–B linkages analogous to those of proposed CO2 insertion intermediate.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.