The new imino sulfinamidine ligand PhS(NHt-Bu)=NC(Me)=N(C6H3-2,6-iPr(2)), LH (11) was synthesized from N-(2,6-diisopropylphenyl)acetamidine (9) and N-tert-butyl phenylsulfinimidoyl chloride (10). Reaction of LH (11) with ZnEt2 or AIMe(3) gave the complexes LZnEt (12) and LAIMe(2) (13), respectively. The structures of 12 and 13 were determined by X-ray diffraction and were shown to contain L as a k(2)-N-1,N-5 bidentate ligand in a six-membered chelate. Formation of the magnesium complex (LMgN(TMS)(2)(L2Mg)-L-.) (14) from 11, Mgl(2), and KN(SiMe3)(2) highlighted a secondary coordination mode of L, binding through the sulfinamidine nitrogens in a four-membered chelate.