Guo, Zhifang, Wang, Nicole, Blair, Victoria L., Izgorodina, Ekaterina I., Deacon, Glen B., and Junk, Peter C. (2022) Facile synthesis and structures of silver formamidinates and pyrazolates. Australian Journal of Chemistry, 75 (8 & 9). pp. 558-565.

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Abstract

Dinuclear silver formamidinates, [Ag₂(DFForm)₂(py)₂] (1) (DFForm, N,N′-bis(2,6-difluorophenyl)formamidinate, py = pyridine), [Ag₂(mHForm)₂(py)₃] (2) and [Ag₂(mHForm)₂(CH3CN)₂] (2a) (mHForm, N,N′-bis(2,3,4,6-tetrafluorophenyl)formamidinate), [Ag₂(pHForm)₂(py)₃] (3) (pHForm, N,N′-bis(2,3,5,6-tetrafluorophenyl)formamidinate), [Ag₂(PFForm)₂(py)₃] (4) (PFForm, N,N′-bis(2,3,4,5,6-pentafluorophenyl)formamidinate) and [Ag₂(DippForm)₂]·1.25CH₂Cl₂ (5) (DippForm, N,N′-bis(2,6-diisopropylphenyl)formamidinate), and polynuclear, mainly trinuclear, silver pyrazolates, [Ag₃(Ph₂pz)₃]₂ (6) (Ph₂pz, 3,5-diphenylpyrazolate), [Ag(tBu₂pz)]₄ (7) (tBu₂pz, 3,5-di-tert-butylpyrazolate), [Ag₃(PhMepz)₃] (8) (PhMepz, 3-methyl-5-phenylpyrazolate), [Ag₃(Phtpz)₃] (9) (Phtpz, 3-phenyl-5-(2-thienyl)pyrazolate), [Ag₃(ttfpz)₃] (10) (ttfpz, 3-(2-thienyl)-5-trifluoromethylpyrazolate) and [Ag₂(Me₂pz)(PPh₃)₄Cl] (11) (Me₂pz, 3,5-dimethylpyrazolate) were successfully synthesized in good yield by treating silver(i) oxide with the corresponding formamidines (FormH) or pyrazoles (pzH) either in pyridine or acetonitrile. These rapid, easily handled and economical reactions are readily monitored by consumption of black silver oxide. All compounds are potential precursors in redox transmetallation reactions in the synthesis of lanthanoid and alkaline earth pyrazolate and formamidinate complexes.

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