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Title: Relativistic effects in metallocorroles: comparison of molybdenum and tungsten biscorroles

Abstract

We present the homoleptic sandwich compounds-Mo and W biscorroles-have afforded a novel platform for experimental studies of relativistic effects. A 200 mV difference in reduction potential and a remarkable 130 nm shift of a near-IR spectral feature have been identified as manifestations of relativistic effects on the properties of these complexes.

Authors:
 [1];  [1];  [2]; ORCiD logo [1]
  1. The Arctic University of Norway (Norway). Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1437954
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 53; Journal Issue: 43; Related Information: © 2017 The Royal Society of Chemistry.; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Alemayehu, Abraham B., Vazquez-Lima, Hugo, McCormick, Laura J., and Ghosh, Abhik. Relativistic effects in metallocorroles: comparison of molybdenum and tungsten biscorroles. United States: N. p., 2017. Web. doi:10.1039/c7cc01549f.
Alemayehu, Abraham B., Vazquez-Lima, Hugo, McCormick, Laura J., & Ghosh, Abhik. Relativistic effects in metallocorroles: comparison of molybdenum and tungsten biscorroles. United States. doi:10.1039/c7cc01549f.
Alemayehu, Abraham B., Vazquez-Lima, Hugo, McCormick, Laura J., and Ghosh, Abhik. Fri . "Relativistic effects in metallocorroles: comparison of molybdenum and tungsten biscorroles". United States. doi:10.1039/c7cc01549f. https://www.osti.gov/servlets/purl/1437954.
@article{osti_1437954,
title = {Relativistic effects in metallocorroles: comparison of molybdenum and tungsten biscorroles},
author = {Alemayehu, Abraham B. and Vazquez-Lima, Hugo and McCormick, Laura J. and Ghosh, Abhik},
abstractNote = {We present the homoleptic sandwich compounds-Mo and W biscorroles-have afforded a novel platform for experimental studies of relativistic effects. A 200 mV difference in reduction potential and a remarkable 130 nm shift of a near-IR spectral feature have been identified as manifestations of relativistic effects on the properties of these complexes.},
doi = {10.1039/c7cc01549f},
journal = {ChemComm},
number = 43,
volume = 53,
place = {United States},
year = {2017},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Figures / Tables:

Table 1 Table 1: Soret and Q maxima (nm), redox potentials (V), and electrochemical HOMOLUMO gaps (V) of M[TpXPC]2 (M = Mo, W) as a function of X.

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Works referenced in this record:

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Substituent effects on metallocorrole spectra: insights from chromium-oxo and molybdenum-oxo triarylcorroles
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5d Early-Transition-Metal Corroles: a Trioxo-Bridged Binuclear Tungsten(VI) Derivative
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    Works referencing / citing this record:

    CCDC 1534096: Experimental Crystal Structure Determination: HAPVEC : bis(5,10,15-tris(4-methylphenyl)corrolato)-molybdenum(vi) dichloromethane solvate
    dataset, February 2017

    • Alemayehu, Abraham B.; Vazquez-Lima, Hugo; McCormick, Laura J.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/ccdc.csd.cc1nhbzg

    Oxidative Metalation as a Route to Size-Mismatched Macrocyclic Complexes: Osmium Corroles
    journal, October 2014

    • Alemayehu, Abraham B.; Gagnon, Kevin J.; Terner, James
    • Angewandte Chemie International Edition, Vol. 53, Issue 52
    • DOI: 10.1002/anie.201405890

    Gold(I) and Gold(III) Corroles
    journal, October 2011

    • Rabinovich, Elena; Goldberg, Israel; Gross, Zeev
    • Chemistry - A European Journal, Vol. 17, Issue 44
    • DOI: 10.1002/chem.201102348

    Metal-Ligand Misfits: Facile Access to Rhenium-Oxo Corroles by Oxidative Metalation
    journal, December 2015

    • Einrem, Rune F.; Gagnon, Kevin J.; Alemayehu, Abraham B.
    • Chemistry - A European Journal, Vol. 22, Issue 2
    • DOI: 10.1002/chem.201504307

    Tungsten Biscorroles: New Chiral Sandwich Compounds
    journal, April 2016

    • Alemayehu, Abraham B.; Vazquez-Lima, Hugo; Gagnon, Kevin J.
    • Chemistry - A European Journal, Vol. 22, Issue 20
    • DOI: 10.1002/chem.201504848

    Synthesis and Molecular Structure of 99 Tc Corroles
    journal, November 2016

    • Einrem, Rune F.; Braband, Henrik; Fox, Thomas
    • Chemistry - A European Journal, Vol. 22, Issue 52
    • DOI: 10.1002/chem.201605015

    Dependence of relativistic effects on electronic configuration in the neutral atoms of d- and f-block elements
    journal, April 2002

    • Autschbach, J.; Siekierski, S.; Seth, M.
    • Journal of Computational Chemistry, Vol. 23, Issue 8
    • DOI: 10.1002/jcc.10060

    Chemistry with ADF
    journal, January 2001

    • te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
    • Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
    • DOI: 10.1002/jcc.1056

    Why is the molybdenum-substituted tungsten-dependent formaldehyde ferredoxin oxidoreductase not active? A quantum chemical study
    journal, November 2012


    Hexacarbonyls of Mo, W, and Sg: Metal–CO Bonding Revisited
    journal, January 2017


    Stepwise Deoxygenation of Nitrite as a Route to Two Families of Ruthenium Corroles: Group 8 Periodic Trends and Relativistic Effects
    journal, April 2017


    Relativistic effects on chemical properties
    journal, August 1979


    Range-Separated Exchange Functionals with Slater-Type Functions
    journal, February 2012

    • Seth, Michael; Ziegler, Tom
    • Journal of Chemical Theory and Computation, Vol. 8, Issue 3
    • DOI: 10.1021/ct300006h

    Relativistic Effects and the Chemistry of the Heaviest Main-Group Elements
    journal, November 2005

    • Thayer, John S.
    • Journal of Chemical Education, Vol. 82, Issue 11
    • DOI: 10.1021/ed082p1721

    Synthesis and Molecular Structure of Gold Triarylcorroles
    journal, December 2011

    • Thomas, Kolle E.; Alemayehu, Abraham B.; Conradie, Jeanet
    • Inorganic Chemistry, Vol. 50, Issue 24
    • DOI: 10.1021/ic202023r

    5d Early-Transition-Metal Corroles: a Trioxo-Bridged Binuclear Tungsten(VI) Derivative
    journal, January 2012

    • Nigel-Etinger, Izana; Goldberg, Israel; Gross, Zeev
    • Inorganic Chemistry, Vol. 51, Issue 4
    • DOI: 10.1021/ic202325h

    Nature and Strength of Metal−Chalcogen Multiple Bonds in High Oxidation State Complexes
    journal, April 1998

    • González-Blanco, Òscar; Branchadell, Vicenç; Monteyne, Kereen
    • Inorganic Chemistry, Vol. 37, Issue 8
    • DOI: 10.1021/ic970613l

    The Metal Carbon Double Bond in Fischer Carbenes: A Density Functional Study of the Importance of Nonlocal Density Corrections and Relativistic Effects
    journal, November 1994

    • Jacobsen, Heiko; Schreckenbach, Georg; Ziegler, Tom
    • The Journal of Physical Chemistry, Vol. 98, Issue 44
    • DOI: 10.1021/j100095a024

    Iridium Corroles
    journal, June 2008

    • Palmer, Joshua H.; Day, Michael W.; Wilson, Aaron D.
    • Journal of the American Chemical Society, Vol. 130, Issue 25
    • DOI: 10.1021/ja801049t

    Molecular structure of a gold β-octakis(trifluoromethyl)- meso -triarylcorrole: an 85° difference in saddling dihedral relative to copper
    journal, April 2012


    Relativistic Effects in Chemistry: More Common Than You Thought
    journal, May 2012


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.