Abstract
A new series of N-benzyl aliphatic N2S tridentate proligands HLn (n = 2–4) derived from 2-[(2-mercaptoethyl)aminomethyl]pyridine (HL1) has been prepared via the sequential reactions of trimethylsilylation, N-benzylation, and hydrolysis. A previously reported aromatic N2S tridentate proligand, 2-[(2-mercaptophenyl)aminomethyl]pyridine (HL5), is also employed as an ancillary ligand. Reaction of these proligands HLn (n = 1–5) with [WO2Cl2(DME)] (DME = 1,2-dimethoxyethane) in the presence of triethylamine leads to the formation of cis-dioxotungsten(VI) complexes [WO2(Ln)Cl] (n = 1–5). Treatment of the chloro derivatives [WO2(Ln)Cl] (n = 1, 5) with the Grignard reagents RMgX (R = CH2SiMe3, C6H4 tBu-4; X = Cl, Br) resulted in ligand substitution reaction and the formation of the first reported alkyl complexes of the type [WO2(Ln)R] (n = 1, 5; R = CH2SiMe3, C6H4 tBu-4).

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