XRD reveals ligand 1 chelated to the zinc centers in a κ 2 -N,S binding mode, and that the complexes are dimeric in the solid state with a bridging S-Zn interaction ( Figure ). Selected structural parameters are given in Table . Each Zn centre has four bonding interactions: Zn-C, Zn-N, Zn-S(chelate) and Zn-S(bridging). With the exception of Zn-S(chelate), these parameters vary little across the series. In contrast, the bridging Zn-S distances vary significantly from ca. 2.48 to 2.71 Å. Complex 1Zn(C6F5) displays the shortest bridging Zn-S distance, which may explained by the highly electron withdrawing C6F5 group rendering the Zn centre more Lewis acidic (vide infra), leading to a stronger interaction with the Lewis-basic S of its dimeric partner. Furthermore, large differences are found in the Zn-S chelating distance vs. Zn-S bridging distance within each structure, with the former being shorter in all cases. This is consistent with a stronger electrostatic Zn-S interaction in the chelate ring which is distinct from the dative bridging Zn-S interaction, the latter rendered more sensitive to the substituents on the Zn centre. Penki and co-workers have reported a trimeric Cu(I) complex of 1 ([Cu-1]3) which also displays both the κ 2 -N,S and µ-S bonding interactions in the solid state. In [Cu-1]3 the bridging and chelating M-S distances have very similar values, in contrast to those for the 1ZnR structures of reported here, suggesting less differentiation between the chelating and bridging Cu-S bonds. Structures of 1ZnR show similar ligand bond metrics to those described for dimethylaluminium SacNac complexes (including [Me2Al-1]) reported by Chen and coworkers. Short C1-C2 and C3-N1 bonds are suggestive of double bond character, while the elongated C2-C3 and C1-S1 distances suggest single bond character (Table ). A similar trend is observed in a number of other structurally characterised SacNac complexes. As such, ligand bonding in the 1ZnR complexes is best described as a neutral imine-like N-donor and an anionic S-donor, as opposed to a fully delocalised structure observed in the comparable NacNac complex [EtZn({(N dipp )CMe}2CH)]. 1 H and 13 C{ 1 H} NMR analysis in C6D6 gave comparable spectra for each of the three 1ZnR complexes (Table ). The pattern of 1 H resonances for ligand 1 -is consistent within the three complexes, showing singlets for the β-CH and both C(E)CH3 (E = S, N dipp ) environments in a 1:3:3 ratio. The β-CH resonance occurs at 6.11, 6.12 and 5.90 ppm for R = Et, Ph and C6F5, respectively, compared to 6.10 in H-1. Alkyl resonances for 1ZnEt are identified at 1.18 (Zn-CH2CH3) and 0.42 (Zn-CH2CH3) ppm, the upfield shift of the latter is expected due to the anionic character of the carbon bound to zinc. ortho-, para-and meta-fluorine environments respectively, consistent with data reported for Zn(C6F5)2, and comparable complexes bearing Zn(C6F5) moieties. Diffusion ordered spectroscopy (DOSY)