Di(tert-butyl)sulfur diimide and bis(trimethylsilyl)sulfur diimide were reacted with different metalated amines to form versatile novel multidentate ligand systems with side-arm donation. Their complexation properties in terms of ligand design, denticity and the cation size are discussed. We report herein the synthesis and structure elucidation of [(tBuN)(2)S{LiMe(2)N(C(6)H(4))S(NtBu)(2)}(2)] (1), [(Li{Me(2)N(C(6)H(4))S(NSiMe(3))(2)})(2)] (2), [(Li(thf){Me(2)N(C(6)H(4))S(NSiMe(3))(2)})(2)] (3), [(Li{2-PicS(NSiMe(3))(2)})(2)] (4), [(Li{Me(2)N(CH(2))(2)N(Me)S(NSiMe(3))(2)})(2)] (5), [(Na{Me(2)N(CH(2))(2)N(Me)S(NSiMe(3))(2)})(2)] (6) and [(K{Me(2)N(C(6)H(4))S(NSiMe(3))(2)})(2)] (7).
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