Geminally Diaurated Aryls Bridged by Semirigid Phosphine Pillars: Syntheses and Electronic Structure |
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| Authors: | Amberle R Browne Dr Nihal Deligonul Bryce L Anderson Prof Arnold L Rheingold Prof Thomas G Gray |
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| Institution: | 1. Department of Chemistry, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106 (USA);2. Present address: Gaziosmanpasa University, Art and Science Faculty, Department of Chemistry, Tokat (Turkey);3. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138 (USA);4. UCSD Crystallography Facility, Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093‐0343 (USA) |
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| Abstract: | Geminally diaurated μ2‐aryl complexes have been prepared where gold(I) centers were bridged by the semirigid diphosphine ligands bis(2‐diphenylphosphinophenyl)ether (DPEphos) and 4,6‐bis(diphenylphosphanyl)dibenzob,d]furan (DBFphos). Diaurated complexes were synthesized in ligand redistribution reactions of the corresponding di‐gold dichlorides with di‐gold diaryls (six of them new) and silver(I) salts. Diaurated complexes were isolated as salts of the minimally coordinating anions SbF6? and ReO4?. Efforts to prepare salts of the tetraarylborate B(3,5‐(CF3)2C6H3)4]? led to transmetalation from boron, with crystallization of the fluorinated aryl complex. The new complexes were characterized by multinuclear NMR, absorption and emission spectroscopies, 77 K emission lifetimes, and by combustion analysis; three are crystallographically characterized. Structures of geminally diaurated aryl ligands are compared to those of mono‐aurated analogues. Both crystal structures and density‐functional theory calculations indicate slight but observable disruptions of aryl ligand aromaticity by geminal di‐gold binding. An intermolecular aurophilic interaction in one structurally authenticated complex was examined computationally. |
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| Keywords: | aromaticity aurophilicity density functional calculations gold phosphine ligands |
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