Probing Fe–V Bonding in a C3-Symmetric Heterobimetallic Complex

Greer, Samuel M.; McKay, Johannes; Gramigna, Kathryn M.; Thomas, Christine M.; Stoian, Sebastian A.; Hill, Stephen

doi:10.1021/acs.inorgchem.8b00280

Title: Probing Fe–V Bonding in a C₃-Symmetric Heterobimetallic Complex

Journal Article · 29 April 2018 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.8b00280 · OSTI ID:1524784

^[1]; McKay, Johannes ^[2]; Gramigna, Kathryn M. ^[3];

^[4];

^[5];

^[2]

Florida State Univ., Tallahassee, FL (United States); Ohio State University
Florida State Univ., Tallahassee, FL (United States)
Brandeis Univ., Waltham, MA (United States)
Brandeis Univ., Waltham, MA (United States); The Ohio State Univ., Columbus, OH (United States)
Florida State Univ., Tallahassee, FL (United States); Univ. of Idaho, Moscow, ID (United States)

Direct metal–metal bonding of two distinct first-row transition metals remains relatively unexplored compared to their second- and third-row heterobimetallic counterparts. Herein, a recently reported Fe–V triply bonded species, [V(ⁱPrNPPh₂)₃FeI] (1; Kuppuswamy, S.; Powers, T. M.; Krogman, J. P.; Bezpalko, M. W.; Foxman, B. M.; Thomas, C. M. Vanadium–iron complexes featuring metal–metal multiple bonds. Chem. Sci.2013, 4, 3557–3565), is studied using high-frequency electron paramagnetic resonance, field- and temperature-dependent ⁵⁷Fe nuclear gamma resonance (Mössbauer) spectroscopy, and high-field electron-electron double resonance detected nuclear magnetic resonance. From the use of this suite of physical methods, we have observed the electronic structure of 1. These studies allow us to establish the effective $$ \tilde{g} $$ tensors as well as the Fe/V electro-nuclear hyperfine interaction tensors of the spin S = 1/2 ground state. We have rationalized these tensors in the context of ligand field theory supported by quantum chemical calculations. This theoretical analysis suggests that the S = 1/2 ground state originates from a single unpaired electron predominately localized on the Fe site.

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Research Organization:: Brandeis Univ., Waltham, MA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0014151

OSTI ID:: 1524784

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 57; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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ELDOR-detected NMR beyond hyperfine couplings: a case study with Cu(ii)-porphyrin dimers Wili, Nino; Richert, Sabine; Limburg, Bart ETH Zurich https://doi.org/10.3929/ethz-b-000345208	text	January 2019

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