Sulfur Lone Pairs Control Topology in Heterotrimetallic Complexes: An Experimental and Theoretical Study

Heterotrimetallic complexes with (N₂S₂)M metallodithiolates, M = Ni²⁺, [Fe(NO)]²⁺, and [Co(NO)]²⁺, as bidentate chelating ligands to a central trans-Cr(NO)(MeCN) unit were characterized as the first members of a new class, NiCrNi, FeCrFe, CoCrCo. The complexes exhibit a cisoid structural topology, ascribed to the stereoactivity of the available lone pair(s) on the sulfur donors, resulting in a dispersed, electropositive pocket from the N/N and N/S hydrocarbon linkers wherein the Cr-NO site is housed. Computational studies explored alternative isomers (transoid and inverted cisoid) that suggest a combination of electronic and steric effects govern the geometrical selectivity. Electrostatic potential maps readily display the dominant electronegative potential from the sulfurs which force the NO to the electropositive pocket. The available S lone pairs work in synergy with the π-withdrawing ability of NO to lift Cr out of the S₄ plane toward the NO and stabilize the geometry. The metallodithiolate ligands bound to Cr(NO) thus find structural consistency across the three congeners. Although the dinitrosyl [(bme-dach)Co(NO)-Mo(NO)(MeCN)-(bme-dach)Co(MeCN)][PF₆]₂ (CoMoCo') analogue displays chemical noninnocence and a partial Mo-Co bond toward (N₂S₂)Co'(NCCH₃) in an "asymmetric butterfly" topology [Guerrero-Almaraz P.Inorg. Chem.2021, 60(21 (21), ), 15975-15979], the stability of the {Cr(NO)}⁵ unit prohibits such bond rearrangement. Magnetism and EPR studies illustrate spin coupling across the sulfur thiolate sulfur bridges.