Martina Landrini, Rohan Patel, Joshua Tyrrell-Thrower, Alceo Macchioni, David L Hughes, Leonardo Tensi, Peter Hrobárik, Luca Rocchigiani
{"title":"探索配体对二茂钼和二茂钨的阳离子金(I)桥氢化物配合物的结构、键合和光解氢转移的影响。","authors":"Martina Landrini, Rohan Patel, Joshua Tyrrell-Thrower, Alceo Macchioni, David L Hughes, Leonardo Tensi, Peter Hrobárik, Luca Rocchigiani","doi":"10.1021/acs.inorgchem.4c01655","DOIUrl":null,"url":null,"abstract":"<p><p>A diverse family of heterobimetallic bridging hydride adducts of the type [LAu(μ-H)<sub>2</sub>MCp<sub>2</sub>][X] (L = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene, IPr; 1,3-bis(1-adamantyl)imidazole-2-ylidene, IAd; 1,3-bis(2,6-di-<i>iso</i>-propylphenyl)-5,5-dimethyl-4,6-diketopyrimidinyl-2-ylidene, <sup>Dipp</sup>DAC; triphenylphosphine, PPh<sub>3</sub>; 2-di-<i>tert</i>-butylphosphino-2',4',6'-triisopropylbiphenyl, <sup><i>t</i>Bu</sup>XPhos; X = SbF<sub>6</sub><sup>-</sup>, BF<sub>4</sub><sup>-</sup> or TfO<sup>-</sup>) was synthesized by reacting group VI metallocene dihydrides Cp<sub>2</sub>MH<sub>2</sub> (Cp = cyclopentadienyl anion; M = Mo, W) with cationic gold(I) complexes [LAu(NCMe)][X]. Trimetallic [L'Au<sub>2</sub>(μ-H)<sub>2</sub>WCp<sub>2</sub>][X]<sub>2</sub> and tetrametallic [L'Au<sub>2</sub>{(μ-H)<sub>2</sub>WCp<sub>2</sub>}<sub>2</sub>] [X]<sub>2</sub> complexes (L' = <i>rac</i>-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene or bis(diphenylphosphinomethane)) were obtained by reacting digold [L'{Au(NCMe)}<sub>2</sub>][X]<sub>2</sub> with Cp<sub>2</sub>WH<sub>2</sub> in a 1:1 and a 1:2 stoichiometry. Accessing such a broad structural diversity allowed us to pinpoint roles played by the ancillary ligands and group VI metals on the bonding properties of this family of bridging hydrides. In particular, a clear effect of the ligand on the interaction energy and electronic structure was observed, with important implications on photolytic reactivity. UV or visible light irradiation, indeed, leads to the selective cleavage of the heterobimetallic Au(μ-H)<sub>2</sub>M arrangement and formation of molecular gold hydrides. The photolysis was found to be chromoselective (wavelength-dependent), which can be ascribed to different charge redistributions upon excitation to the first (Kasha's reactivity) and higher (anti-Kasha's reactivity) excited states.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3000,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Exploring Ligand Effects on Structure, Bonding, and Photolytic Hydride Transfer of Cationic Gold(I) Bridging Hydride Complexes of Molybdocene and Tungstenocene.\",\"authors\":\"Martina Landrini, Rohan Patel, Joshua Tyrrell-Thrower, Alceo Macchioni, David L Hughes, Leonardo Tensi, Peter Hrobárik, Luca Rocchigiani\",\"doi\":\"10.1021/acs.inorgchem.4c01655\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>A diverse family of heterobimetallic bridging hydride adducts of the type [LAu(μ-H)<sub>2</sub>MCp<sub>2</sub>][X] (L = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene, IPr; 1,3-bis(1-adamantyl)imidazole-2-ylidene, IAd; 1,3-bis(2,6-di-<i>iso</i>-propylphenyl)-5,5-dimethyl-4,6-diketopyrimidinyl-2-ylidene, <sup>Dipp</sup>DAC; triphenylphosphine, PPh<sub>3</sub>; 2-di-<i>tert</i>-butylphosphino-2',4',6'-triisopropylbiphenyl, <sup><i>t</i>Bu</sup>XPhos; X = SbF<sub>6</sub><sup>-</sup>, BF<sub>4</sub><sup>-</sup> or TfO<sup>-</sup>) was synthesized by reacting group VI metallocene dihydrides Cp<sub>2</sub>MH<sub>2</sub> (Cp = cyclopentadienyl anion; M = Mo, W) with cationic gold(I) complexes [LAu(NCMe)][X]. Trimetallic [L'Au<sub>2</sub>(μ-H)<sub>2</sub>WCp<sub>2</sub>][X]<sub>2</sub> and tetrametallic [L'Au<sub>2</sub>{(μ-H)<sub>2</sub>WCp<sub>2</sub>}<sub>2</sub>] [X]<sub>2</sub> complexes (L' = <i>rac</i>-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene or bis(diphenylphosphinomethane)) were obtained by reacting digold [L'{Au(NCMe)}<sub>2</sub>][X]<sub>2</sub> with Cp<sub>2</sub>WH<sub>2</sub> in a 1:1 and a 1:2 stoichiometry. Accessing such a broad structural diversity allowed us to pinpoint roles played by the ancillary ligands and group VI metals on the bonding properties of this family of bridging hydrides. In particular, a clear effect of the ligand on the interaction energy and electronic structure was observed, with important implications on photolytic reactivity. UV or visible light irradiation, indeed, leads to the selective cleavage of the heterobimetallic Au(μ-H)<sub>2</sub>M arrangement and formation of molecular gold hydrides. The photolysis was found to be chromoselective (wavelength-dependent), which can be ascribed to different charge redistributions upon excitation to the first (Kasha's reactivity) and higher (anti-Kasha's reactivity) excited states.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2024-07-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.inorgchem.4c01655\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/7/11 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.inorgchem.4c01655","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/7/11 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Exploring Ligand Effects on Structure, Bonding, and Photolytic Hydride Transfer of Cationic Gold(I) Bridging Hydride Complexes of Molybdocene and Tungstenocene.
A diverse family of heterobimetallic bridging hydride adducts of the type [LAu(μ-H)2MCp2][X] (L = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene, IPr; 1,3-bis(1-adamantyl)imidazole-2-ylidene, IAd; 1,3-bis(2,6-di-iso-propylphenyl)-5,5-dimethyl-4,6-diketopyrimidinyl-2-ylidene, DippDAC; triphenylphosphine, PPh3; 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, tBuXPhos; X = SbF6-, BF4- or TfO-) was synthesized by reacting group VI metallocene dihydrides Cp2MH2 (Cp = cyclopentadienyl anion; M = Mo, W) with cationic gold(I) complexes [LAu(NCMe)][X]. Trimetallic [L'Au2(μ-H)2WCp2][X]2 and tetrametallic [L'Au2{(μ-H)2WCp2}2] [X]2 complexes (L' = rac-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene or bis(diphenylphosphinomethane)) were obtained by reacting digold [L'{Au(NCMe)}2][X]2 with Cp2WH2 in a 1:1 and a 1:2 stoichiometry. Accessing such a broad structural diversity allowed us to pinpoint roles played by the ancillary ligands and group VI metals on the bonding properties of this family of bridging hydrides. In particular, a clear effect of the ligand on the interaction energy and electronic structure was observed, with important implications on photolytic reactivity. UV or visible light irradiation, indeed, leads to the selective cleavage of the heterobimetallic Au(μ-H)2M arrangement and formation of molecular gold hydrides. The photolysis was found to be chromoselective (wavelength-dependent), which can be ascribed to different charge redistributions upon excitation to the first (Kasha's reactivity) and higher (anti-Kasha's reactivity) excited states.
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.