Heteroleptic gold complexes with 4,5-diselenolate-1,3-dithiole-2-thione (C3S3Se2(super2-), dsit)

Article Abstract:

The reaction of (NBu4)2(Zn(dsit)2) (where dsit is 4,5-diselenolate-1,3-dithiole-2-thione) with AuClL, when the ration is 1:4, yields (Au2(dsit)L2) (L is PPh3 (1), PPh2Me(2)), and the diselenolate group is transfered. The 2 complex reacts then with (Au(OClO3)L) in equimolar quantities to give the trinuclear (Au3(dsit)(PPh2Me)3)ClO4 (3), a complex. In a 1:2 ratio, the reaction of (NBu4)2(Zn(dsit)2) with (Au2Cl2(P-P) resulting complexes are (Au2(dsit)(P-P))n (P-P is dppe (1,2-bis(diphenylphosphine)ethane), n = 1; P-P = dppm (bis(diphenylphosphine)methane), n = 2). Anionic derivatives would be obtained by reaction of the zinc complex in 1:1 ratio with (NBu4)(AuBr4. Other gold complexes must have a tin complex for ligand transfer.

Tin compounds, Organometallic compounds, Gold compounds

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Identity-reaction proton transfers from nitrogen acids yielding localized vs. delocalized conjugate bases: an ab initio study

Article Abstract:

Identity-reaction proton transfers to the corresponding conjugate bases for a group of nitrogen acids have been studied using ab initio methods. At the G2(MP2) level, gas-phase acidities were calculated to get benchmark values for each acidity. Experimental values are not available at that level. Barriers to proton transfer related to separated reactants indicate a straight-line relationship with acidity for the neutral acids and the cationic acids, with the exception of four of them.

Molecular electronics, Protons, Nitrogen compounds, Organic acids

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