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Title: Actinide 2-metallabiphenylenes that satisfy Hückel’s rule

Journal Article · · Nature (London)
 [1];  [2];  [3];  [3];  [3];  [3];  [4];  [3];  [3];  [5];  [3]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Vermont, Burlington, VT (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States); Beijing Inst. of Technology (China)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Univ. of Vermont, Burlington, VT (United States)
  5. Univ. of Minnesota, Minneapolis, MN (United States)
+ Show Author Affiliations

Aromaticity and antiaromaticity, as defined by Hückel’s rule, are key ideas in organic chemistry, and are both exemplified in biphenylene—a molecule that consists of two benzene rings joined by a four-membered ring at its core. Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) π-electron system have so far been associated only with organic compounds. In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead. Here we report the synthesis and characterization of, to our knowledge, the first 2-metallabiphenylene compounds. Single-crystal X-ray diffraction studies reveal that these complexes have nearly planar, 11-membered metallatricycles with metrical parameters that compare well with those reported for biphenylene. Nuclear magnetic resonance spectroscopy, in addition to nucleus-independent chemical shift calculations, provides evidence that these complexes contain an antiaromatic cyclobutadiene ring and an aromatic benzene ring. Finally, spectroscopic evidence, Kohn–Sham molecular orbital compositions and natural bond orbital calculations suggest covalency and delocalization of the uranium f2 electrons with the carbon-containing ligand.

Research Organization:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
SC0002183; CHE-1265608; CHE-1565658; AC06-05OR231100; AC52-06NA25396
OSTI ID:
1605163
Journal Information:
Nature (London), Vol. 578, Issue 7796; ISSN 0028-0836
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 29 works
Citation information provided by
Web of Science

References (58)

Generalized Gradient Approximation Made Simple journal October 1996
Tetraphenyldihydrocyclobutaarenes—what causes the extremely long 1.72 Å C–C single bond? journal January 1998
Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory journal March 2015
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides journal September 1976
[(C5Me5)2U][(µ-Ph)2BPh2] as a four electron reductant journal January 2005
Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C 5 Me 5 ) 2 U(μ-H)] 2 journal February 2016
Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl 6 2– (M = Ti, Zr, Hf, U) and UOCl 5 – Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory journal March 2012
Naphthocyclobutenes and Benzodicyclobutadienes: Synthesis in the Solid State and Anomalies in the Bond Lengths journal April 2000
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species journal August 2009
Orbital Crossings Activated through Electron Injection: Opening Communication between Orthogonal Orbitals in Anionic C1–C5 Cyclizations of Enediynes journal November 2016
Systematic Studies of Early Actinide Complexes:  Uranium(IV) Fluoroketimides journal September 2007
Quantum electrodynamical corrections to the fine structure of helium journal January 1974
Second‐order perturbation theory with a complete active space self‐consistent field reference function journal January 1992
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions journal January 1980
Main Group Atoms and Dimers Studied with a New Relativistic ANO Basis Set December 2003
Aqueous coordination chemistry and photochemistry of uranyl(vi) oxalate revisited: a density functional theory study journal January 2010
Nucleus-Independent Chemical Shifts:  A Simple and Efficient Aromaticity Probe journal January 1996
Applicability of the no-pair equation with free-particle projection operators to atomic and molecular structure calculations journal August 1985
Evidence for the Involvement of 5f Orbitals in the Bonding and Reactivity of Organometallic Actinide Compounds: Thorium(IV) and Uranium(IV) Bis(hydrazonato) Complexes journal December 2008
Unbiased auxiliary basis sets for accurate two-electron integral approximations journal September 2007
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) journal July 2004
Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations journal November 1990
Molecular Spectroscopy of Uranium(IV) Bis(ketimido) Complexes. Rare Observation of Resonance-Enhanced Raman Scattering from Organoactinide Complexes and Evidence for Broken-Symmetry Excited States journal January 2005
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
New relativistic ANO basis sets for actinide atoms journal June 2005
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
A thorium metallacyclopentadiene complex: a combined experimental and computational study journal January 2015
Actinide–Silicon Multiradical Bonding: Infrared Spectra and Electronic Structures of the Si(μ-X)AnF 3 (An = Th, U; X = H, F) Molecules journal January 2014
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach journal May 1980
Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C5Me5)2U(η4-1,2,3,4-PhC4Ph) journal February 2017
Osteopontin: A Uranium Phosphorylated Binding-Site Characterization journal July 2013
Magnetic Shielding, Aromaticity, Antiaromaticity, and Bonding in the Low-Lying Electronic States of Benzene and Cyclobutadiene journal October 2016
Interactions of 1-Methylimidazole with UO 2 (CH 3 CO 2 ) 2 and UO 2 (NO 3 ) 2 :  Structural, Spectroscopic, and Theoretical Evidence for Imidazole Binding to the Uranyl Ion journal January 2007
A refinement of the structure of biphenylene journal January 1966
Benzo[3,4]cyclobuta[1,2-c]thiophen (2-thianorbiphenylene) journal January 1970
The Induced Magnetic Field in Cyclic Molecules journal September 2004
Calculation of Dipole-Forbidden 5f Absorption Spectra of Uranium(V) Hexa-Halide Complexes journal February 2018
Heliphenes and Related Structures journal September 2011
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions journal November 2006
Toward reliable density functional methods without adjustable parameters: The PBE0 model journal April 1999
New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory journal January 2014
Actinide Redox-Active Ligand Complexes: Reversible Intramolecular Electron-Transfer in U(dpp-BIAN) 2 /U(dpp-BIAN) 2 (THF) journal February 2010
Biphenylene journal May 1941
Synthesis and X-ray Structure of a Zirconocene Complex of Two Alkynes journal June 1994
Second-order perturbation theory with a CASSCF reference function journal July 1990
Organometallic Uranium(V)−Imido Halide Complexes: From Synthesis to Electronic Structure and Bonding journal April 2008
Energy-Degeneracy-Driven Covalency in Actinide Bonding journal December 2018
Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds journal November 1981
Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8 journal November 2015
Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex journal May 2014
Phenylsilane as a safe, versatile alternative to hydrogen for the synthesis of actinide hydrides journal January 2015
Trends in Electronic Structure and Redox Energetics for Early-Actinide Pentamethylcyclopentadienyl Complexes journal October 2004
Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials journal January 2003
What a Difference a 5f Element Makes: Trivalent and Tetravalent Uranium Halide Complexes Supported by One and Two Bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) Ligands journal March 2009
Thorium(IV) and Uranium(IV) Ketimide Complexes Prepared by Nitrile Insertion into Actinide−Alkyl and −Aryl Bonds journal September 2004
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules journal March 1972
Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex journal May 2014

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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