ABSTRACT
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.
ABSTRACT
Two synthetic approaches to install metallodithiolate ligands on molybdenum centers using the synthons [Mo2(CH3CN)10]4+ and (N2S2)Co(NO) [N2S2 = N,N-bis(2-mercaptoethyl)-1,4-diazacycloheptane and NO = nitric oxide], or [Mo(NO)2(CH3CN)4]2+ (CH3CN = acetonitrile) and [(N2S2)Co]2 lead to a bis-nitrosylated, trimetallic dication, CoMoCo'. This unique asymmetric butterfly complex, with S = 1, has a bent NO within the small {Co(NO)}8 wing (denoted as Co), reflecting CoIII(NO-), and is S-bridged to a linear {Mo(NO)}6 diamagnetic unit. The latter is further S-bridged to a pentacoordinate (N2S2)CoIII(CH3CN) donor in the larger wing and is the origin of the two unpaired electrons, denoted as Co'. The asymmetry in Mo-Co distances, 3.33 Å in the Co wing and 2.73 Å in the Co' wing, indicated a Mo-Co' bonding interaction. The transfer of NO from (N2S2)Co(NO) in the former path is needed to cleave the strong quadruple bond in [Moâ£Mo]4+, with the energetic cost compensated for via a one-electron bond between Mo and Co', as indicated by natural bonding orbital analysis.
