A sequence of first row transition metal(II) dithiolates M(SAr*)(2) (M = Cr(1), Mn(2), Fe(3), Co(4), Ni(5) and Zn(6); Ar* = C6H3-2,6-(C6H2-2,4,6-Pr-3(i))2) has been synthesized and characterized. Compounds 1-5 were obtained by the reaction of two equiv of LiSAr* with a metal dihalide, whereas 6 was obtained by treatment of ZnMe2 with 2 equiv of HSAr*. They were characterized by spectroscopy, magnetic measurements, and X-ray crystallography. The dithiolates 1, 2, and 4-6 possess linear or nearly linear SMS units with further interactions between M and two ipso carbons from C6H2-2,4,6-Pr-3(i) rings. The iron species 3, however, has a bent geometry, two different Fe-S distances, and an interaction between iron and one ipso carbon of a flanking ring. The secondary M-C interactions vary in strength in the sequence Cr2+ approximate to Fe2+ > Co2+ approximate to Ni2+ > Mn2+ approximate to Zn2+ Sue h that the manganese and zinc compounds have essentially two coordination but the chromium and iron complexes are quasi four and three coordinate, respectively. The geometric distortions in the iron species 3 suggested that the structure represents the initial stage of a rearrangement into a sandwich structure involving metal-aryl ring coordination. The bent structure of 3 probably also precludes the observation of free ion magnetism of Fe2+ recently reported for Fe{C(SiMe3)(3)}(2). DFT calculations on the model compounds M(SPh)(2) (M = Cr-Ni) support the higher tendency of the iron species to distort its geometry.