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

Journal Article · · ChemComm
DOI:https://doi.org/10.1039/c7cc01549f· OSTI ID:1437954
 [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)

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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1437954
Journal Information:
ChemComm, Vol. 53, Issue 43; Related Information: © 2017 The Royal Society of Chemistry.; ISSN 1359-7345
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

References (33)

Range-Separated Exchange Functionals with Slater-Type Functions journal February 2012
Iridium Corroles journal June 2008
Platinum corroles journal January 2014
Stepwise Deoxygenation of Nitrite as a Route to Two Families of Ruthenium Corroles: Group 8 Periodic Trends and Relativistic Effects journal April 2017
Stabilization of high oxidation states in transition metals. An electrochemical and computational study of structurally comparable molybdenum and tungsten complexes journal January 1996
Synthesis and reactivity of tantalum corrole complexes journal January 2017
Gold corroles journal February 2011
Chemistry with ADF journal January 2001
Substituent effects on metallocorrole spectra: insights from chromium-oxo and molybdenum-oxo triarylcorroles journal November 2011
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
Oxidative Metalation as a Route to Size-Mismatched Macrocyclic Complexes: Osmium Corroles journal October 2014
Relativistic effects on chemical properties journal August 1979
Metal-Ligand Misfits: Facile Access to Rhenium-Oxo Corroles by Oxidative Metalation journal December 2015
Synthesis and Molecular Structure of Gold Triarylcorroles journal December 2011
Relativistic Effects in Chemistry: More Common Than You Thought journal May 2012
Synthesis and Molecular Structure of 99 Tc Corroles journal November 2016
Dependence of relativistic effects on electronic configuration in the neutral atoms of d- and f-block elements journal April 2002
Relativistic effects in iron-, ruthenium-, and osmium porphyrins journal December 2002
Gold(I) and Gold(III) Corroles journal October 2011
Relativistic Effects and the Chemistry of the Heavier Main Group Elements book January 2010
Molecular structure of a gold β-octakis(trifluoromethyl)- meso -triarylcorrole: an 85° difference in saddling dihedral relative to copper journal April 2012
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
5d Early-Transition-Metal Corroles: a Trioxo-Bridged Binuclear Tungsten(VI) Derivative journal January 2012
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
Tungsten Biscorroles: New Chiral Sandwich Compounds journal April 2016
Why is the molybdenum-substituted tungsten-dependent formaldehyde ferredoxin oxidoreductase not active? A quantum chemical study journal November 2012
Preparation and characterization of a tungsten(V) corrole dichloride complex journal January 2015
Electronic Structure of Corrole Derivatives: Insights from Molecular Structures, Spectroscopy, Electrochemistry, and Quantum Chemical Calculations journal November 2016
Hexacarbonyls of Mo, W, and Sg: Metal–CO Bonding Revisited journal January 2017
Relativistic Effects and the Chemistry of the Heaviest Main-Group Elements journal November 2005
Nature and Strength of Metal−Chalcogen Multiple Bonds in High Oxidation State Complexes journal April 1998
Oxidative Metalation as a Route to Size-Mismatched Macrocyclic Complexes: Osmium Corroles journal October 2014
Relativistic effects on chemical properties journal February 1983

Cited By (1)



Figures / Tables (5)


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