Sarah Costa, Sarah M. Chui, Katelyn A. Espinoza, James C. Fettinger, Alan L. Balch
{"title":"Bridging 1,2-Bis(diphenylphosphino)methane Ligands Facilitate the Formation of Binuclear Complexes with Both Two-Coordinate and Three-Coordinate Gold(I) Ions","authors":"Sarah Costa, Sarah M. Chui, Katelyn A. Espinoza, James C. Fettinger, Alan L. Balch","doi":"10.1021/acs.inorgchem.4c03657","DOIUrl":null,"url":null,"abstract":"Five new crystalline gold(I) complexes β-Au<sub>2</sub>(μ-dppm)<sub>2</sub>Br<sub>2</sub>·2CH<sub>2</sub>Cl<sub>2</sub> (<b>1</b>), [Au<sub>2</sub>(μ- dppm)<sub>2</sub>Br]Br·2CH<sub>2</sub>Cl<sub>2</sub> (<b>2</b>), [Au<sub>2</sub>(μ-dppm)<sub>2</sub>Br](PF<sub>6</sub>) (<b>3</b>), [Au<sub>2</sub>(μ-dppm)<sub>2</sub>Cl](BPh<sub>4</sub>)·3CH<sub>2</sub>Cl<sub>2</sub> (<b>4</b>) and [Au<sub>2</sub>(μ-dppm)<sub>2</sub>]Cl(AsF<sub>6</sub>)·2CH<sub>2</sub>Cl<sub>2</sub> (<b>5</b>) (where dppm is bis(diphenylphosphino)methane) have been prepared and structurally characterized by single crystal X-ray diffraction. Colorless β-Au<sub>2</sub>(μ-dppm)<sub>2</sub>Br<sub>2</sub>·2CH<sub>2</sub>Cl<sub>2</sub> (<b>1</b>) has centrosymmetric structure with two three-coordinate gold(I) ions held in close proximity by the dppm ligands. Crystals of [Au<sub>2</sub>(μ- dppm)<sub>2</sub>Br]Br·2CH<sub>2</sub>Cl<sub>2</sub> (<b>2</b>), [Au<sub>2</sub>(μ-dppm)<sub>2</sub>Br](PF<sub>6</sub>) (<b>3</b>), and [Au<sub>2</sub>(μ-dppm)<sub>2</sub>Cl](BPh<sub>4</sub>)·3CH<sub>2</sub>Cl<sub>2</sub> (<b>4</b>) have a cation with an unusual arrangement that binds a two-coordinate gold(I) ion to a three-coordinate gold(I) ion through an aurophilic interaction. Whereas Au<sub>2</sub>(μ-dppm)<sub>2</sub>Cl(BPh<sub>4</sub>)·3CH<sub>2</sub>Cl<sub>2</sub> (<b>4</b>) has a chloride ion bound to only one of the gold ions in the complex, [Au<sub>2</sub>(μ-dppm)<sub>2</sub>]Cl(AsF<sub>6</sub>)·2CH<sub>2</sub>Cl<sub>2</sub> (<b>5</b>) has an ion paired chloride ion that is symmetrically disposed between the two gold ions at a rather long distance. Each complex displays luminescence under UV irradiation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"115 1","pages":""},"PeriodicalIF":4.3000,"publicationDate":"2024-12-18","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.4c03657","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Bridging 1,2-Bis(diphenylphosphino)methane Ligands Facilitate the Formation of Binuclear Complexes with Both Two-Coordinate and Three-Coordinate Gold(I) Ions
Five new crystalline gold(I) complexes β-Au2(μ-dppm)2Br2·2CH2Cl2 (1), [Au2(μ- dppm)2Br]Br·2CH2Cl2 (2), [Au2(μ-dppm)2Br](PF6) (3), [Au2(μ-dppm)2Cl](BPh4)·3CH2Cl2 (4) and [Au2(μ-dppm)2]Cl(AsF6)·2CH2Cl2 (5) (where dppm is bis(diphenylphosphino)methane) have been prepared and structurally characterized by single crystal X-ray diffraction. Colorless β-Au2(μ-dppm)2Br2·2CH2Cl2 (1) has centrosymmetric structure with two three-coordinate gold(I) ions held in close proximity by the dppm ligands. Crystals of [Au2(μ- dppm)2Br]Br·2CH2Cl2 (2), [Au2(μ-dppm)2Br](PF6) (3), and [Au2(μ-dppm)2Cl](BPh4)·3CH2Cl2 (4) have a cation with an unusual arrangement that binds a two-coordinate gold(I) ion to a three-coordinate gold(I) ion through an aurophilic interaction. Whereas Au2(μ-dppm)2Cl(BPh4)·3CH2Cl2 (4) has a chloride ion bound to only one of the gold ions in the complex, [Au2(μ-dppm)2]Cl(AsF6)·2CH2Cl2 (5) has an ion paired chloride ion that is symmetrically disposed between the two gold ions at a rather long distance. Each complex displays luminescence under UV irradiation.
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.