An improved synthesis of lithium phenyltris(methimazolyl)borate, Li[PhTmMe], (methimazole = 1-methylimidazole2-thione) is described, and the structure of the methanol-solvated [Li(OHMe)(4)][PhTmMe] has been determined. The syntheses and characterization of complexes [M(PhTmMe)(PR3)] (M = Cu, Ag, Au; R = Et, Ph;) are reported, and the complexes [Cu(PhTmMe)(PPh3)], [Ag(PhTmMe)(PEt3)] and [Au(PhTmMe)(PEt3)] are crystallographically characterized, showing a progression from pseudo-tetrahedral geometry (copper, S3\P coordination) to trigonal planar geometry (silver, S2P coordination) to linear geometry (gold, SP coordination). In addition, the copper(l) and silver(l) triphenylphosphine complexes of the adventitiously formed phenylhydrobis(methimazolyl)borate ligand, [M(PhBm(Me))-(PPh3)], have been crystallographically characterized, showing both species to have a trigonal planar primary coordination sphere, with a secondary (MH)-H-...-B interaction. Finally, reaction of copper(II) chloride with Li[PhTmMe] results in formation of a compound analyzing as [Cu-II(PhTmMe)Cl], although its extreme insolubility and marked instability have precluded its complete characterization. Attempts to prepare this by ultra-slow diffusion of the reactants through solvent blanks has led to isolation of a mixed-valence copper(I/II) methimazolate cluster, [Cu-10(1)-Cu-2(II) (mt)(12)Cl-2] and a copper(l) dimeric complex [Cu-2(PhTmme)(2)], indicating that copper(II) ions oxidatively decompose the phenyltris(methimazolyl)borate anion.