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Desulfurization can outcompete dehydration in microdroplets, enabling catalyst-free, selective formation of pharmaceutically relevant 1,3,4-oxadiazolesviathiol oxidation at the air–water interface. 

ABSTRACT: Heterotrimetallic complexes with (N2S2)M metal- lodithiolates, 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, electropositivepocketfromtheN/NandN/Shydrocarbonlinkers whereintheCr-NOsiteishoused.Computationalstudiesexploredalternativeisomers(transoidandinvertedcisoid)thatsuggesta 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 workinsynergywiththeπ-withdrawingabilityofNOtoliftCroutoftheS4 planetowardtheNOandstabilizethegeometry.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 andapartialMo−Cobondtoward(N2S2)Co′(NCCH3)inan“asymmetricbutterfly”topology[Guerrero-Almaraz,P.etal.Inorg. Chem. 2021, 60(2121), 15975−15979], the stability of the {Cr(NO)}5 unit prohibits such bond rearrangement. Magnetism and EPRstudiesillustratespincouplingacrossthesulfurthiolatesulfurbridges. KEYWORDS: metallodithiolate, topology, chromium, sulfur, computations, hydrocarbon cavity