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Mohammad A. Omary Department of Chemistry, University of North Texas (from my post-doctoral work with Professor John Fackler at Texas A&M University)

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Presentation on theme: "Mohammad A. Omary Department of Chemistry, University of North Texas (from my post-doctoral work with Professor John Fackler at Texas A&M University)"— Presentation transcript:

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2 Mohammad A. Omary Department of Chemistry, University of North Texas (from my post-doctoral work with Professor John Fackler at Texas A&M University)

3 Gold Starting material in Fackler’s lab

4 Trinuclear Au(I) Complexes, TRAu: TRAu + M +  ??? M=Ag; Tl

5 IT’S A WHOPPER!!

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7 Synthetic Strategy Burini; Fackler; Omary’s; Staples et al. Inorg. Chem.2000, 39, 3158. TRAu + M +  {(TRAu) 2 M + } 

8 Burini; Fackler; Omary; Staples, et al. Inorg. Chem.2000, 39, 3158.

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10 * Nucleophilic or basic character to the trinuclear gold complexes. Analogy with cation-  interactions: Dennis A. Dougherty, Science 1996, 271, 163. Why not a neutral Lewis acid ? - TRHg:Hg 3 (C 6 F 4 ) 3

11 OR Intercalates TRHg {(TRAu) 2 (TRHg)} 

12 SUPER WHOPPER!!

13 Burini; Fackler; Omary; Staples et al. J. Am. Chem. Soc. 2000, 122, 11264-11265. SUPRAMOLECULAR CHAIN ASSEMBLIES

14 {(TR(carb)) 2 (TRHg)} 

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16 DFT Calculations of Trinuclear Complexes Electrost. Pot. (a.u.) -0.0300 0.0300 [Au(bzim)] 3 [Hg(C 6 F 4 )] 3

17 green = positive [Au(bzim)] 3 red = negative Electrostatic Potential Surfaces  Electrostatic interaction

18 ADF Calculations [Au(carb)] 3 MONOMER -15 Electrost. Pot. (kcal) +15

19 ADF Calculations {[Au(carb)] 3 } 2 DIMER -15 Electrost. Pot. (kcal) +15 Full Range (kcal/mol): +23  -46 for dimer +22  -34 for monomer

20 AD F Calculations {[Au(carb)] 3 } 2 DIMER Green= positive Red=negative

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22 Raman spectrum of a solution of TR(carb) in CH 2 Cl 2 at RT

23 Perhaps, closed-shell metallophilic interactions play a role in stabilizing the supramolecular structure!! Ultimate test for the basic behavior: ==> ORGANIC LEWIS ACIDS: C 6 F 6 ; TCNQ

24 3.152 Å Intramolecular Au…Au: 3.475; 3.471; 3.534 Å 3.152 Å Charge transfer complex indicated by: - shortening of Au..Au - intense color…. Omary; Fackler et al. J. Am. Chem. Soc. 2001, 123, 9689-9691.

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