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]
- The Arctic University of Norway (Norway). Department of Chemistry and Center for Theoretical and Computational Chemistry, UiT
- 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}
}
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Cited by: 6 works
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Figures / Tables:
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:
Range-Separated Exchange Functionals with Slater-Type Functions
journal, February 2012
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A Reassessment of the First Metal-Carbonyl Dissociation Energy in M(CO)4 (M = Ni, Pd, Pt), M(CO)5 (M = Fe, Ru, Os), and M(CO)6 (M = Cr, Mo, W) by a Quasirelativistic Density Functional Method
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5d Early-Transition-Metal Corroles: a Trioxo-Bridged Binuclear Tungsten(VI) Derivative
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Metal-Ligand Misfits: Facile Access to Rhenium-Oxo Corroles by Oxidative Metalation
journal, December 2015
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Tungsten Biscorroles: New Chiral Sandwich Compounds
journal, April 2016
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- Chemistry - A European Journal, Vol. 22, Issue 20
Why is the molybdenum-substituted tungsten-dependent formaldehyde ferredoxin oxidoreductase not active? A quantum chemical study
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- JBIC Journal of Biological Inorganic Chemistry, Vol. 18, Issue 2
Preparation and characterization of a tungsten(V) corrole dichloride complex
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Synthesis and Molecular Structure of Gold Triarylcorroles
journal, December 2011
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- Inorganic Chemistry, Vol. 50, Issue 24
Electronic Structure of Corrole Derivatives: Insights from Molecular Structures, Spectroscopy, Electrochemistry, and Quantum Chemical Calculations
journal, November 2016
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Relativistic Effects in Chemistry: More Common Than You Thought
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Hexacarbonyls of Mo, W, and Sg: Metal–CO Bonding Revisited
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- Iliaš, Miroslav; Pershina, Valeria
- Inorganic Chemistry, Vol. 56, Issue 3
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
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
Synthesis and Molecular Structure of 99 Tc Corroles
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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)
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
Gold(I) and Gold(III) Corroles
journal, October 2011
- Rabinovich, Elena; Goldberg, Israel; Gross, Zeev
- Chemistry - A European Journal, Vol. 17, Issue 44
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
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
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
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
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
Why is the molybdenum-substituted tungsten-dependent formaldehyde ferredoxin oxidoreductase not active? A quantum chemical study
journal, November 2012
- Liao, Rong-Zhen
- JBIC Journal of Biological Inorganic Chemistry, Vol. 18, Issue 2
Electronic Structure of Corrole Derivatives: Insights from Molecular Structures, Spectroscopy, Electrochemistry, and Quantum Chemical Calculations
journal, November 2016
- Ghosh, Abhik
- Chemical Reviews, Vol. 117, Issue 4
Hexacarbonyls of Mo, W, and Sg: Metal–CO Bonding Revisited
journal, January 2017
- Iliaš, Miroslav; Pershina, Valeria
- Inorganic Chemistry, Vol. 56, Issue 3
Stepwise Deoxygenation of Nitrite as a Route to Two Families of Ruthenium Corroles: Group 8 Periodic Trends and Relativistic Effects
journal, April 2017
- Alemayehu, Abraham B.; Vazquez-Lima, Hugo; Gagnon, Kevin J.
- Inorganic Chemistry, Vol. 56, Issue 9
Relativistic effects on chemical properties
journal, August 1979
- Pitzer, Kenneth S.
- Accounts of Chemical Research, Vol. 12, Issue 8
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
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
Synthesis and Molecular Structure of Gold Triarylcorroles
journal, December 2011
- Thomas, Kolle E.; Alemayehu, Abraham B.; Conradie, Jeanet
- Inorganic Chemistry, Vol. 50, Issue 24
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
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
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
A Reassessment of the First Metal-Carbonyl Dissociation Energy in M(CO)4 (M = Ni, Pd, Pt), M(CO)5 (M = Fe, Ru, Os), and M(CO)6 (M = Cr, Mo, W) by a Quasirelativistic Density Functional Method
journal, January 1995
- Li, Jian; Schreckenbach, Georg; Ziegler, Tom
- Journal of the American Chemical Society, Vol. 117, Issue 1
Theoretical study on the quadruple metal bond in d4-d4 binuclear tetracarboxylate complexes of chromium, molybdenum, and tungsten by the Hartree-Fock-Slater transition-state method
journal, July 1985
- Ziegler, Tom
- Journal of the American Chemical Society, Vol. 107, Issue 15
Iridium Corroles
journal, June 2008
- Palmer, Joshua H.; Day, Michael W.; Wilson, Aaron D.
- Journal of the American Chemical Society, Vol. 130, Issue 25
Molecular structure of a gold β-octakis(trifluoromethyl)- meso -triarylcorrole: an 85° difference in saddling dihedral relative to copper
journal, April 2012
- Thomas, Kolle E.; Beavers, Christine M.; Ghosh, Abhik
- Molecular Physics, Vol. 110, Issue 19-20
Relativistic Effects in Chemistry: More Common Than You Thought
journal, May 2012
- Pyykkö, Pekka
- Annual Review of Physical Chemistry, Vol. 63, Issue 1
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.