Role of Hydrogen Bond in the Synthesis and Complexation of Diphenylsulfilimine Ph2S → NH

New synthesis of the mixed bis-acetylacetonate complexes of Co, Ni and Zn bearing 1 or 2 diphenylsulfilimine ligands Ph2S -> NH (2) is described. Improved synthetic protocol towards anhydrous ligand 2 was developed. Earlier known Ph2S = NTs forms upon acid hydrolysis easily extractable, air -stable and non -hygroscopic tosylate salt [Ph2SNH2]+TsO (1), that crystallize as dimer stabilized by hydrogen bonds in the solid state and can serve as stable and storable precursor for preparation on demand of labile ligand 2. Non-nucleophilic bases in dry ether or aromatic solvents when reacted with 1 provide 2 in high yields. Monomeric CoII (4), ZnII (5) and NiII (6) bis- acetylacetonate dihydrates when reacted with 2 form mixed complexes M(acac)2(Ph2SNH) 7, M = Zn; 8, M = Co and Ni(acac)2(Ph2SNH)2 9 in up to 90 % yields. Molecular structure of dimeric {CoII(acac)2(Ph2SNH)}2 complex (8) reveals strong donor Co -N interactions stabilized by intramolecular O & sdot;& sdot;& sdot;H-N hydrogen bonds between acacligands and the H-N group of Ph2S -> NH (2).