Assessing the Metal–Metal Interactions in a Series of Heterobimetallic Nb/M Complexes (M = Fe, Co, Ni, Cu) and Their Effect on Multielectron Redox Properties

Barden, Brett A.; Culcu, Gursu; Krogman, Jeremy P.; Bezpalko, Mark W.; Hatzis, Gregory P.; Dickie, Diane A.; Foxman, Bruce M.; Thomas, Christine M.

doi:10.1021/acs.inorgchem.8b02960

Title: Assessing the Metal–Metal Interactions in a Series of Heterobimetallic Nb/M Complexes (M = Fe, Co, Ni, Cu) and Their Effect on Multielectron Redox Properties

Journal Article · Thu Dec 20 00:00:00 EST 2018 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.8b02960· OSTI ID:1524782

Barden, Brett A. ^[1]; Culcu, Gursu ^[2]; Krogman, Jeremy P. ^[2]; Bezpalko, Mark W. ^[2]; Hatzis, Gregory P. ^[1];

^[2];

^[3]

The Ohio State Univ., Columbus, OH (United States)
Brandeis Univ., Waltham, MA (United States)
The Ohio State Univ., Columbus, OH (United States); Brandeis Univ., Waltham, MA (United States)

A one-pot synthetic procedure for a series of bimetallic Nb/M complexes, Cl–Nb(ⁱPrNPPh₂)₃M–X (M = Fe (2), Ni (4), Cu (5)), is introduced. A similar procedure aimed at synthesizing a Nb/Co analogue instead affords ⁱPrN=Nb(iPrNPPh₂)₂(μ-PPh₂)Co–I (3) through cleavage of one phosphinoamide P–N bond under reducing conditions. Complexes 4 and 5 are found to have short Nb-M distances, corresponding to unusual metal–metal bonds between Nb and these first row transition metals. For comparison, a series of heterobimetallic O≡Nb(ⁱPrNPPh₂)₃M–X complexes (M = Fe (7), Co (8), Ni (9), Cu (10)) was synthesized. In these complexes, the Nb^V center is engaged in sufficient π-bonding to the terminal oxo ligand to remove the driving force for direct metal–metal interactions. A comparison of the cyclic voltammograms of 2 and 4–10 shows that the presence of a second metal shifts the redox potentials of both Nb and the late metal center anodically, even when direct metal–metal interactions are not present.

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Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: SC0019179; SC0014151

OSTI ID:: 1524782

Journal Information:: Inorganic Chemistry, Vol. 58, Issue 1; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 9 works

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CCDC 1873734: Experimental Crystal Structure Determination Barden, Brett A.; Culcu, Gursu; Krogman, Jeremy P. https://doi.org/10.5517/ccdc.csd.cc20ws1r The current record is supplemented by this dataset	dataset	January 2018
CCDC 1873735: Experimental Crystal Structure Determination Barden, Brett A.; Culcu, Gursu; Krogman, Jeremy P. https://doi.org/10.5517/ccdc.csd.cc20ws2s The current record is supplemented by this dataset	dataset	January 2018
CCDC 1873736: Experimental Crystal Structure Determination Barden, Brett A.; Culcu, Gursu; Krogman, Jeremy P. https://doi.org/10.5517/ccdc.csd.cc20ws3t The current record is supplemented by this dataset	dataset	January 2018
CCDC 1873732: Experimental Crystal Structure Determination Barden, Brett A.; Culcu, Gursu; Krogman, Jeremy P. https://doi.org/10.5517/ccdc.csd.cc20wrzn The current record is supplemented by this dataset	dataset	January 2018

Title: Assessing the Metal–Metal Interactions in a Series of Heterobimetallic Nb/M Complexes (M = Fe, Co, Ni, Cu) and Their Effect on Multielectron Redox Properties

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