Formation of Gold(III) Alkyls from Gold Alkoxide Complexes

The gold(III) methoxide complex (C∧N∧C)AuOMe (1) reacts with tris(p-tolyl)phosphine in benzene at room temperature under O abstraction to give the methylgold product (C∧N∧C)AuMe (2) together with O=P(p-tol)3 ((C∧N∧C) = [2,6-(C6H3t Bu-4)2pyridine]2-). Calculations show that this reaction is energetically favorable (ΔG = -32.3 kcal mol-1). The side products in this reaction, the Au(II) complex [Au(C∧N∧C)]2 (3) and the phosphorane (p-tol)3P(OMe)2, suggest that at least two reaction pathways may operate, including one involving (C∧N∧C)Au• radicals. Attempts to model the reaction by DFT methods showed that PPh3 can approach 1 to give a near-linear Au-O-P arrangement, without phosphine coordination to gold. The analogous reaction of (C∧N∧C)AuOEt, on the other hand, gives exclusively a mixture of 3 and (p-tol)3P(OEt)2. Whereas the reaction of (C∧N∧C)AuOR (R = But, p-C6H4F) with P(p-tol)3 proceeds over a period of hours, compounds with R = CH2CF3, CH(CF3)2 react almost instantaneously, to give 3 and O=P(p-tol)3. In chlorinated solvents, treatment of the alkoxides (C∧N∧C)AuOR with phosphines generates [(C∧N∧C)Au(PR3)]Cl, via Cl abstraction from the solvent. Attempts to extend the synthesis of gold(III) alkoxides to allyl alcohols were unsuccessful; the reaction of (C∧N∧C)AuOH with an excess of CH2=CHCH2OH in toluene led instead to allyl alcohol isomerization to give a mixture of gold alkyls, (C∧N∧C)AuR' (R' = -CH2CH2CHO (10), -CH2CH(CH2OH)OCH2CH=CH2 (11)), while 2-methallyl alcohol affords R' = CH2CH(Me)CHO (12). The crystal structure of 11 was determined. The formation of Au-C instead of the expected Au-O products is in line with the trend in metal-ligand bond dissociation energies for Au(III): M-H > M-C > M-O.