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

Guerrero-Almaraz, Paulina; Quiroz, Manuel; Rodriguez, David R.; Jana, Manish; Hall, Michael B.; Darensbourg, Marcetta Y.

doi:10.1021/acsorginorgau.3c00025

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

Journal Article · 13 September 2023 · ACS Organic & Inorganic Au

DOI: https://doi.org/10.1021/acsorginorgau.3c00025 · OSTI ID:2000232

Guerrero-Almaraz, Paulina ^[1]; Quiroz, Manuel ^[1]; Rodriguez, David R. ^[1]; Jana, Manish ^[1];

^[1];

^[1]

Texas A&M University, College Station, TX (United States)

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, 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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Reconfigurable Electronic Materials Inspired by Nonlinear Neuron Dynamics (REMIND); Texas A&M Engineering Experiment Station; Texas A&M University, College Station, TX (United States)

Sponsoring Organization:: Basic Energy Sciences; Division of Chemistry; USDOE Office of Science (SC), Basic Energy Sciences (BES); Welch Foundation

Grant/Contract Number:: SC0023353

OSTI ID:: 2000232

Journal Information:: ACS Organic & Inorganic Au, Journal Name: ACS Organic & Inorganic Au Journal Issue: 6 Vol. 3; ISSN 2694-247X

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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CCDC 2221527: Experimental Crystal Structure Determination Paulina, Guerrero-Almaraz,; Manuel, Quiroz,; R., Rodriguez, David https://doi.org/10.5517/ccdc.csd.cc2dkp5v The current record is supplemented by this dataset	dataset	January 2023
CCDC 2221528: Experimental Crystal Structure Determination Paulina, Guerrero-Almaraz,; Manuel, Quiroz,; R., Rodriguez, David https://doi.org/10.5517/ccdc.csd.cc2dkp6w The current record is supplemented by this dataset	dataset	January 2023
CCDC 2221529: Experimental Crystal Structure Determination Paulina, Guerrero-Almaraz,; Manuel, Quiroz,; R., Rodriguez, David https://doi.org/10.5517/ccdc.csd.cc2dkp7x The current record is supplemented by this dataset	dataset	January 2023

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

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