Pushing the Limits of Delta Bonding in Metal–Chromium Complexes with Redox Changes and Metal Swapping

Eisenhart, Reed J.; Rudd, P. Alex; Planas, Nora; Boyce, David W.; Carlson, Rebecca K.; Tolman, William B.; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C.

doi:10.1021/acs.inorgchem.5b01163

Title: Pushing the Limits of Delta Bonding in Metal–Chromium Complexes with Redox Changes and Metal Swapping

Journal Article · Mon Jul 13 00:00:00 EDT 2015 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5b01163· OSTI ID:1370563

Eisenhart, Reed J. ^[1]; Rudd, P. Alex ^[1]; Planas, Nora ^[1]; Boyce, David W. ^[1]; Carlson, Rebecca K. ^[1]; Tolman, William B. ^[1]; Bill, Eckhard ^[2]; Gagliardi, Laura ^[1]; Lu, Connie C. ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Max Planck Institut für Chemische Energiekonversion (MPI-CEC), Ruhr (Germany)

Into the metalloligand Cr[N(o-(NCH₂P(ⁱPr)₂)C₆H₄)₃] (1, CrL) was inserted a second chromium atom to generate the dichromium complex Cr₂L (2), which is a homobimetallic analogue of the known MCrL complexes, where M is manganese (3) or iron (4). The cationic and anionic counterparts, [MCrL]⁺ and [MCrL]^-, respectively, were targeted, and each MCr pair was isolated in at least one other redox state. The solid-state structures of the [MCrL]^+,0,– redox members are basically the same, with ultrashort metal–metal bonds between 1.96 and 1.74 Å. The formal shortness ratios (r) of these interactions are between 0.84 and 0.74 and are interpreted as triple to quintuple metal–metal bonds with the aid of theory. The trio of (d–d)¹⁰ species [Cr₂L]^- (₂red), MnCrL (3), and [FeCrL]⁺ (4^ox) are S = 0 diamagnets. On the basis of M—Cr bond distances and theoretical calculations, the strength of the metal–metal bond across the (d–d)¹⁰ series increases in the order Fe < Mn < Cr. The methylene protons in the ligand are shifted downfield in the 1H NMR spectra, and the diamagnetic anisotropy of the metal–metal bond was calculated as -3500 × 10^–36, -3900 × 10^–36, and -5800 × 10^–36 m³ molecule^–1 for 2^red, 3, and 4^ox respectively. The magnitude of diamagnetic anisotropy is, thus, affected more by bond polarity than by bond order. A comparative vis–NIR study of quintuply bonded 2^red and 3 revealed a large red shift in the δ⁴ → δ³δ^* transition energy upon swapping from the (Cr₂)²⁺ to the (MnCr)³⁺ core. Complex 2^red was further investigated by resonance Raman spectroscopy, and a band at 434 cm^–1 was assigned as the Cr—Cr bond vibration. Lastly, 4^ox exhibited a Mössbauer doublet with an isomer shift of 0.18 mm/s that suggests a primarily Fe-based oxidation to Fe(I).

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Institutes of Health (NIH)

Grant/Contract Number:: SC0012702; CHE-1254621

OSTI ID:: 1370563

Journal Information:: Inorganic Chemistry, Vol. 54, Issue 15; Related Information: ICDC partners with University of Minnesota(lead); Argonne National Laboratory; Clemson University; Dow Chemical Company; Northwestern University; Pacific Northwest National Laboratory; University of California Davis; University of Washington; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 42 works

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References (107)

Band Spectra and Chemistry. Mulliken, Robert S. Chemical Reviews, Vol. 6, Issue 4 https://doi.org/10.1021/cr60024a005	journal	January 1930
Bonding Power of Electrons and Theory of Valence. Mulliken, Robert S. Chemical Reviews, Vol. 9, Issue 3 https://doi.org/10.1021/cr60034a001	journal	December 1931
Mononuclear and Polynuclear Chemistry of Rhenium (III): Its Pronounced Homophilicity Cotton, F. A.; Curtis, N. F.; Harris, C. B. Science, Vol. 145, Issue 3638 https://doi.org/10.1126/science.145.3638.1305	journal	September 1964
Compounds Containing Dirheniurm(III) Octahalide Anions Cotton, F. A.; Curtis, N. F.; Johnson, B. F. G. Inorganic Chemistry, Vol. 4, Issue 3 https://doi.org/10.1021/ic50025a014	journal	March 1965
Clusters of transition-metal atoms Morse, Michael D. Chemical Reviews, Vol. 86, Issue 6 https://doi.org/10.1021/cr00076a005	journal	December 1986
Laser vaporization of alloys: Laser induced fluorescence of heteronuclear metal clusters Bondybey, V. E.; Schwartz, G. P.; English, J. H. The Journal of Chemical Physics, Vol. 78, Issue 1 https://doi.org/10.1063/1.444532	journal	January 1983
Bond strengths of transition-metal dimers: titanium-vanadium( TiV), vanadium dimer, titanium-cobalt (TiCo), and vanadium-nickel (VNi) Spain, Eileen M.; Morse, Michael D. The Journal of Physical Chemistry, Vol. 96, Issue 6 https://doi.org/10.1021/j100185a018	journal	March 1992
Analysing the chromium–chromium multiple bonds using multiconfigurational quantum chemistry Brynda, Marcin; Gagliardi, Laura; Roos, Björn O. Chemical Physics Letters, Vol. 471, Issue 1-3 https://doi.org/10.1016/j.cplett.2009.02.006	journal	March 2009
Reaching the Maximum Multiplicity of the Covalent Chemical Bond Roos, Björn O.; Borin, Antonio C.; Gagliardi, Laura Angewandte Chemie International Edition, Vol. 46, Issue 9 https://doi.org/10.1002/anie.200603600	journal	February 2007
The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems Malmqvist, Per Åke; Pierloot, Kristine; Shahi, Abdul Rehaman Moughal The Journal of Chemical Physics, Vol. 128, Issue 20 https://doi.org/10.1063/1.2920188	journal	May 2008
Synthesis of a Stable Compound with Fivefold Bonding Between Two Chromium(I) Centers Nguyen, Tailuan; Sutton, Andrew D.; Brynda, Marcin Science, Vol. 310, Issue 5749 https://doi.org/10.1126/science.1116789	journal	September 2005
To Boldly Pass the Metal–Metal Quadruple Bond Radius, Udo; Breher, Frank Angewandte Chemie International Edition, Vol. 45, Issue 19 https://doi.org/10.1002/anie.200504322	journal	May 2006
Theory, synthesis and reactivity of quintuple bonded complexes Nair, Anokh K.; Harisomayajula, N. V. Satyachand; Tsai, Yi-Chou Dalton Trans., Vol. 43, Issue 15 https://doi.org/10.1039/C3DT53565G	journal	January 2014
Ultrashort metal–metal distances and extreme bond orders Wagner, Frank R.; Noor, Awal; Kempe, Rhett Nature Chemistry, Vol. 1, Issue 7 https://doi.org/10.1038/nchem.359	journal	September 2009
Chromium Mediated Reductive Coupling of Isonitrile Forms Unusual Heterocycles Shen, Jingmei; Yap, Glenn P. A.; Theopold, Klaus H. Journal of the American Chemical Society, Vol. 136, Issue 9 https://doi.org/10.1021/ja501291p	journal	February 2014
Quintuple Bond Reactivity toward Group 16 and 17 Elements: Addition vs Insertion Tamne, Emmanuel Sobgwi; Noor, Awal; Qayyum, Sadaf Inorganic Chemistry, Vol. 52, Issue 1 https://doi.org/10.1021/ic3020805	journal	December 2012
Reactions of Metal-Metal Quintuple Bonds with Alkynes: [2+2+2] and [2+2] Cycloadditions Chen, Hong-Zhang; Liu, Shih-Cheng; Yen, Chun-Hsu Angewandte Chemie International Edition, Vol. 51, Issue 41 https://doi.org/10.1002/anie.201205027	journal	September 2012
Formation of cyclo-E42− Units (E4=P4, As4, AsP3) by a Complex with a CrCr Quintuple Bond Schwarzmaier, Christoph; Noor, Awal; Glatz, Germund Angewandte Chemie International Edition, Vol. 50, Issue 32 https://doi.org/10.1002/anie.201102361	journal	June 2011
Haloacylation of the Quintuple-Bonded Group VI Metal Amidinate Dimers and Disproportionation of Acyl Groups to Form Carbynes Chen, Han-Gung; Hsueh, Hsiang-Wen; Kuo, Ting-Shen Angewandte Chemie International Edition, Vol. 52, Issue 39 https://doi.org/10.1002/anie.201304750	journal	August 2013
Carboalumination of a chromium–chromium quintuple bond Noor, Awal; Glatz, Germund; Müller, Robert Nature Chemistry, Vol. 1, Issue 4 https://doi.org/10.1038/nchem.255	journal	June 2009
Metal–metal multiple bonding in C3-symmetric bimetallic complexes of the first row transition metals Krogman, Jeremy P.; Thomas, Christine M. Chemical Communications, Vol. 50, Issue 40 https://doi.org/10.1039/c3cc47537a	journal	January 2014
A series of C3-symmetric heterobimetallic Cr–M (M = Fe, Co and Cu) complexes Kuppuswamy, Subramaniam; Bezpalko, Mark W.; Powers, Tamara M. Chemical Science, Vol. 5, Issue 4 https://doi.org/10.1039/c3sc52943f	journal	January 2014
Vanadium–iron complexes featuring metal–metal multiple bonds Kuppuswamy, Subramaniam; Powers, Tamara M.; Krogman, Jeremy P. Chemical Science, Vol. 4, Issue 9 https://doi.org/10.1039/c3sc51337h	journal	January 2013
Systematic Variation of Metal–Metal Bond Order in Metal–Chromium Complexes Clouston, Laura J.; Siedschlag, Randall B.; Rudd, P. Alex Journal of the American Chemical Society, Vol. 135, Issue 35 https://doi.org/10.1021/ja406506m	journal	August 2013
Multiple Metal-Metal Bonds in Iron-Chromium Complexes Rudd, P. Alex; Liu, Shengsi; Planas, Nora Angewandte Chemie International Edition, Vol. 52, Issue 16 https://doi.org/10.1002/anie.201208686	journal	March 2013
Metal–Alane Adducts with Zero-Valent Nickel, Cobalt, and Iron Rudd, P. Alex; Liu, Shengsi; Gagliardi, Laura Journal of the American Chemical Society, Vol. 133, Issue 51 https://doi.org/10.1021/ja2099744	journal	December 2011
Synthesis and Structure of the Thallium(I) Salt of the Tetrakis{3,5-bis(trifluoromethyl)phenyl}borate Anion Hughes, Russell P.; Lindner, Danielle C.; Rheingold, Arnold L. Inorganic Chemistry, Vol. 36, Issue 8 https://doi.org/10.1021/ic961164c	journal	April 1997
Synthesis, Reactivity, and Crystal and Molecular Structures of Nb(L)(.eta.6-C6H5-nXn)2B(C6H5-nXn)2, a Class of Mononuclear Metal Compounds Containing the 12-Electron-Donor Tetraarylborato Ligand Calderazzo, Fausto; Pampaloni, Guido; Rocchi, Lucia Organometallics, Vol. 13, Issue 7 https://doi.org/10.1021/om00019a016	journal	July 1994
[(3,5-(CF3)2C6H3)4B]-[H(OEt2)2]+: a convenient reagent for generation and stabilization of cationic, highly electrophilic organometallic complexes Brookhart, M.; Grant, B.; Volpe, A. F. Organometallics, Vol. 11, Issue 11 https://doi.org/10.1021/om00059a071	journal	November 1992
Proton Resonance Shifts in Nickelocene McConnell, H. M.; Holm, C. H. The Journal of Chemical Physics, Vol. 27, Issue 1 https://doi.org/10.1063/1.1743694	journal	July 1957
[16] SHELXL: High-resolution refinement Sheldrick, George M.; Schneider, Thomas R. Methods in Enzymology https://doi.org/10.1016/S0076-6879(97)77018-6	book	January 1997
A short history of SHELX Sheldrick, George M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122 https://doi.org/10.1107/S0108767307043930	journal	December 2007
Structure validation in chemical crystallography Spek, Anthony L. Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155 https://doi.org/10.1107/S090744490804362X	journal	January 2009
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Electronic structure calculations on workstation computers: The program system turbomole Ahlrichs, Reinhart; Bär, Michael; Häser, Marco Chemical Physics Letters, Vol. 162, Issue 3 https://doi.org/10.1016/0009-2614(89)85118-8	journal	October 1989
Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr Schäfer, Ansgar; Huber, Christian; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 100, Issue 8 https://doi.org/10.1063/1.467146	journal	April 1994
Auxiliary basis sets to approximate Coulomb potentials Eichkorn, Karin; Treutler, Oliver; Öhm, Holger Chemical Physics Letters, Vol. 240, Issue 4 https://doi.org/10.1016/0009-2614(95)00621-A	journal	June 1995
Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries Alecu, I. M.; Zheng, Jingjing; Zhao, Yan Journal of Chemical Theory and Computation, Vol. 6, Issue 9 https://doi.org/10.1021/ct100326h	journal	August 2010
Vibrational frequency scale factors for density functional theory and the polarization consistent basis sets Laury, Marie L.; Carlson, Matthew J.; Wilson, Angela K. Journal of Computational Chemistry, Vol. 33, Issue 30 https://doi.org/10.1002/jcc.23073	journal	July 2012
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M. Chemical Physics, Vol. 48, Issue 2 https://doi.org/10.1016/0301-0104(80)80045-0	journal	May 1980
Second‐order perturbation theory with a complete active space self‐consistent field reference function Andersson, Kerstin; Malmqvist, Per‐Åke; Roos, Björn O. The Journal of Chemical Physics, Vol. 96, Issue 2 https://doi.org/10.1063/1.462209	journal	January 1992
Second-order perturbation theory with a CASSCF reference function Andersson, Kerstin.; Malmqvist, Per Aake.; Roos, Bjoern O. The Journal of Physical Chemistry, Vol. 94, Issue 14 https://doi.org/10.1021/j100377a012	journal	July 1990
MOLCAS 7: The Next Generation Aquilante, Francesco; De Vico, Luca; FerrÃ©, Nicolas Journal of Computational Chemistry, Vol. 31, Issue 1 https://doi.org/10.1002/jcc.21318	journal	January 2010
Quantum electrodynamical corrections to the fine structure of helium Douglas, Marvin; Kroll, Norman M. Annals of Physics, Vol. 82, Issue 1 https://doi.org/10.1016/0003-4916(74)90333-9	journal	January 1974
Main Group Atoms and Dimers Studied with a New Relativistic ANO Basis Set Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke https://doi.org/10.1021/jp031064+		December 2003
New Relativistic ANO Basis Sets for Transition Metal Atoms Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke The Journal of Physical Chemistry A, Vol. 109, Issue 29 https://doi.org/10.1021/jp0581126	journal	July 2005
Cholesky Decomposition-Based Multiconfiguration Second-Order Perturbation Theory (CD-CASPT2): Application to the Spin-State Energetics of Co ^III (diiminato)(NPh) Aquilante, Francesco; Malmqvist, Per-Åke; Pedersen, Thomas Bondo Journal of Chemical Theory and Computation, Vol. 4, Issue 5 https://doi.org/10.1021/ct700263h	journal	April 2008
Low-cost evaluation of the exchange Fock matrix from Cholesky and density fitting representations of the electron repulsion integrals Aquilante, Francesco; Pedersen, Thomas Bondo; Lindh, Roland The Journal of Chemical Physics, Vol. 126, Issue 19 https://doi.org/10.1063/1.2736701	journal	May 2007
Accurate ab initio density fitting for multiconfigurational self-consistent field methods Aquilante, Francesco; Pedersen, Thomas Bondo; Lindh, Roland The Journal of Chemical Physics, Vol. 129, Issue 2 https://doi.org/10.1063/1.2953696	journal	July 2008
Local properties of quantum chemical systems: The LoProp approach Gagliardi, Laura; Lindh, Roland; Karlström, Gunnar The Journal of Chemical Physics, Vol. 121, Issue 10 https://doi.org/10.1063/1.1778131	journal	September 2004
Calculation of transition density matrices by nonunitary orbital transformations Malmqvist, Per �ke International Journal of Quantum Chemistry, Vol. 30, Issue 4 https://doi.org/10.1002/qua.560300404	journal	October 1986
The CASSCF state interaction method Malmqvist, Per-Åke; Roos, Björn O. Chemical Physics Letters, Vol. 155, Issue 2 https://doi.org/10.1016/0009-2614(89)85347-3	journal	February 1989
Group 10 and 11 Metal Boratranes (Ni, Pd, Pt, CuCl, AgCl, AuCl, and Au ⁺ ) Derived from a Triphosphine−Borane Sircoglou, Marie; Bontemps, Sébastien; Bouhadir, Ghenwa Journal of the American Chemical Society, Vol. 130, Issue 49 https://doi.org/10.1021/ja8070072	journal	December 2008
The usefulness of EPR spectroscopy in the study of compounds with metal–metal multiple bonds Dalal, Naresh S.; Murillo, Carlos A. Dalton Trans., Vol. 43, Issue 23 https://doi.org/10.1039/C4DT00506F	journal	January 2014
EPR Spectroscopic and Theoretical Study of Chromium(I) Carbonyl Phosphine and Phosphonite Complexes Cummings, Derek A.; McMaster, Jonathan; Rieger, Anne L. Organometallics, Vol. 16, Issue 20 https://doi.org/10.1021/om970252h	journal	September 1997
400. The determination of the paramagnetic susceptibility of substances in solution by nuclear magnetic resonance Evans, D. F. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9590002003	journal	January 1959
Substituent Effects in Formally Quintuple-Bonded ArCrCrAr Compounds (Ar = Terphenyl) and Related Species Wolf, Robert; Ni, Chengbao; Nguyen, Tailuan Inorganic Chemistry, Vol. 46, Issue 26 https://doi.org/10.1021/ic702112e	journal	December 2007
Metal-Metal Distances at the Limit: A Coordination Compound with an Ultrashort Chromium-Chromium Bond Noor, Awal; Wagner, Frank R.; Kempe, Rhett Angewandte Chemie International Edition, Vol. 47, Issue 38 https://doi.org/10.1002/anie.200801160	journal	September 2008
Metal-Metal Distances at the Limit: Cr-Cr 1.73 Å - the Importance of the Ligand and its Fine Tuning Noor, Awal; Glatz, Germund; Müller, Robert Zeitschrift für anorganische und allgemeine Chemie, Vol. 635, Issue 8 https://doi.org/10.1002/zaac.200900175	journal	July 2009
The Ligand-Based Quintuple Bond-Shortening Concept and Some of Its Limitations Noor, Awal; Bauer, Tobias; Todorova, Tanya K. Chemistry - A European Journal, Vol. 19, Issue 30 https://doi.org/10.1002/chem.201301240	journal	July 2013
The Shortest Metal−Metal Bond Yet: Molecular and Electronic Structure of a Dinuclear Chromium Diazadiene Complex Kreisel, Kevin A.; Yap, Glenn P. A.; Dmitrenko, Olga Journal of the American Chemical Society, Vol. 129, Issue 46 https://doi.org/10.1021/ja076356t	journal	November 2007
Quintuply-Bonded Dichromium(I) Complexes Featuring Metal-Metal Bond Lengths of 1.74 Å Hsu, Chia-Wei; Yu, Jen-Shiang K.; Yen, Chun-Hsu Angewandte Chemie International Edition, Vol. 47, Issue 51 https://doi.org/10.1002/anie.200803859	journal	November 2008
Bond Characterization on a Cr–Cr Quintuple Bond: A Combined Experimental and Theoretical Study Wu, Lai-Chin; Hsu, Chia-Wei; Chuang, Yu-Chun The Journal of Physical Chemistry A, Vol. 115, Issue 45 https://doi.org/10.1021/jp203080j	journal	November 2011
Stepwise Construction of the CrCr Quintuple Bond and Its Destruction upon Axial Coordination Huang, Yu-Lun; Lu, Duan-Yen; Yu, Hsien-Cheng Angewandte Chemie International Edition, Vol. 51, Issue 31 https://doi.org/10.1002/anie.201202337	journal	June 2012
Atomic Radii and Interatomic Distances in Metals Pauling, Linus Journal of the American Chemical Society, Vol. 69, Issue 3 https://doi.org/10.1021/ja01195a024	journal	March 1947
Covalent radii revisited Cordero, Beatriz; Gómez, Verónica; Platero-Prats, Ana E. Dalton Transactions, Issue 21 https://doi.org/10.1039/b801115j	journal	January 2008
Triplet state of a binuclear copper dl-tartrate and electron paramagnetic resonance spectra of the copper tartrates Chasteen, N. Dennis; Belford, R. Linn Inorganic Chemistry, Vol. 9, Issue 1 https://doi.org/10.1021/ic50083a033	journal	January 1970
Remarkably Short Metal-Metal Bonds: A Lantern-Type Quintuply Bonded Dichromium(I) Complex Tsai, Yi-Chou; Hsu, Chia-Wei; Yu, Jen-Shiang K. Angewandte Chemie International Edition, Vol. 47, Issue 38 https://doi.org/10.1002/anie.200801286	journal	September 2008
Negative ion photoelectron spectroscopy of chromium dimer Casey, Sean M.; Leopold, Doreen G. The Journal of Physical Chemistry, Vol. 97, Issue 4 https://doi.org/10.1021/j100106a005	journal	January 1993
Electronic structure and vibrational frequency of Cr2 Bondybey, V. E.; English, J. H. Chemical Physics Letters, Vol. 94, Issue 5 https://doi.org/10.1016/0009-2614(83)85029-5	journal	February 1983
The bond length of chromium dimer Michalopoulos, D. L.; Geusic, M. E.; Hansen, S. G. The Journal of Physical Chemistry, Vol. 86, Issue 20 https://doi.org/10.1021/j100217a005	journal	September 1982
Chromium Compounds Cotton, F. Albert Multiple Bonds Between Metal Atoms https://doi.org/10.1007/0-387-25829-9_3	book	January 2005
Physical, Spectroscopic and Theoretical Results Cotton, F. Albert Multiple Bonds Between Metal Atoms https://doi.org/10.1007/0-387-25829-9_16	book	January 2005
Remarkable Effects of Axial π* Coordination on the Cr−Cr Quadruple Bond in Dichromium Paddlewheel Complexes Cotton, F. Albert; Daniels, Lee M.; Murillo, Carlos A. Journal of the American Chemical Society, Vol. 121, Issue 29 https://doi.org/10.1021/ja9912675	journal	July 1999
Elongation of the Quadruple Cr ^II −Cr ^II Bond Induced by Two PtMe ₂ Moieties in the Linearly Aligned Tetrametal System, PtMe ₂ ···Cr−Cr···PtMe ₂ Mashima, Kazushi; Tanaka, Mitsuhiro; Tani, Kazuhide Journal of the American Chemical Society, Vol. 119, Issue 18 https://doi.org/10.1021/ja964052t	journal	May 1997
Diamagnetic anisotropy of metal-metal triple bonds McGlinchey, Michael J. Inorganic Chemistry, Vol. 19, Issue 5 https://doi.org/10.1021/ic50207a060	journal	May 1980
Diamagnetic anisotropy induced by metal-metal multiple bonds San Filippo, Joseph. Inorganic Chemistry, Vol. 11, Issue 12 https://doi.org/10.1021/ic50118a063	journal	December 1972
Diamagnetic anisotropy of the MoMo bond in Mo2(O2CR)4 type complexes Agaskar, Pradyot A.; Albert Cotton, F. Polyhedron, Vol. 5, Issue 3 https://doi.org/10.1016/S0277-5387(00)84455-1	journal	January 1986
Diamagnetic anisotropy of quadruple MoMo bonds: α-Mo2Cl4(diphosphine)2 complexes Cotton, F. Albert; Kitagawa, Susumu Polyhedron, Vol. 7, Issue 18 https://doi.org/10.1016/S0277-5387(00)80397-6	journal	January 1988
A Dichromium(II) Bis(η ⁸ -pentalene) Double-Sandwich Complex with a Spin Equilibrium: Synthetic, Structural, Magnetic, and Theoretical Studies Balazs, Gabor; Cloke, F. Geoffrey N.; Gagliardi, Laura Organometallics, Vol. 27, Issue 9 https://doi.org/10.1021/om701153t	journal	May 2008
Complexes containing heteronuclear quadruple bonds. Preparation and characterization of quadruply bonded .alpha.-MoWCl4(L-L)2 (L-L = dppe, dmpe) and .beta.-MoWCl4(L-L)2 (L-L = dppm, dmpm, dppe) Cotton, F. A.; James, Chris A. Inorganic Chemistry, Vol. 31, Issue 25 https://doi.org/10.1021/ic00051a023	journal	December 1992
Preparation and characterization of two new group VI quadruply bonded dinuclear compounds: Cr2(DFM)4 and W2(DFM)4 Cotton, F. Albert; Ren, Tong Journal of the American Chemical Society, Vol. 114, Issue 6 https://doi.org/10.1021/ja00032a045	journal	March 1992
A new synthetic route to quadruply bonded tungsten-tungsten and molybdenum-tungsten compounds of the type MM'X4(PR3)4, X = Cl or Br. Structural characterization of quadruply bonded WWBr4(.mu.-dppm)2 and MoWBr4(PMe2Ph)4 and phosphorus-31{proton} NMR spectra of these and related compounds Cotton, F. A.; Eglin, Judith L.; James, Chris A. Inorganic Chemistry, Vol. 32, Issue 5 https://doi.org/10.1021/ic00057a031	journal	March 1993
Complexes containing heteronuclear and homonuclear quadruple bonds. Preparation and characterization of bis[bis(dimethylphosphino)methane]tetrachloromolybdenumtungsten and Mo2X4(dmpm)2 (X = bromide, iodide) Cotton, F. A.; Dunbar, K. R.; Hong, B. Inorganic Chemistry, Vol. 32, Issue 23 https://doi.org/10.1021/ic00075a040	journal	November 1993
A Quantum Chemical Study of the Quintuple Bond between Two Chromium Centers in [PhCrCrPh]:trans-Bent versus Linear Geometry Brynda, Marcin; Gagliardi, Laura; Widmark, Per-Olof Angewandte Chemie International Edition, Vol. 45, Issue 23 https://doi.org/10.1002/anie.200600110	journal	June 2006
Bond Length and Bond Order in One of the Shortest Cr−Cr Bonds La Macchia, Giovanni; Aquilante, Francesco; Veryazov, Valera Inorganic Chemistry, Vol. 47, Issue 24 https://doi.org/10.1021/ic801537w	journal	December 2008
On the Analysis of the Cr−Cr Multiple Bond in Several Classes of Dichromium Compounds La Macchia, G.; Li Manni, G.; Todorova, T. K. Inorganic Chemistry, Vol. 49, Issue 11 https://doi.org/10.1021/ic100345b	journal	June 2010
Prediction and interpretation of the 57Fe isomer shift in Mössbauer spectra by density functional theory Neese, Frank Inorganica Chimica Acta, Vol. 337 https://doi.org/10.1016/S0020-1693(02)01031-9	journal	September 2002
An Octahedral Coordination Complex of Iron(VI) Berry, J. F. Science, Vol. 312, Issue 5782 https://doi.org/10.1126/science.1128506	journal	June 2006
Fe-N2/CO complexes that model a possible role for the interstitial C atom of FeMo-cofactor (FeMoco) Rittle, J.; Peters, J. C. Proceedings of the National Academy of Sciences, Vol. 110, Issue 40 https://doi.org/10.1073/pnas.1310153110	journal	September 2013
Triggering N2 uptake via redox-induced expulsion of coordinated NH3 and N2 silylation at trigonal bipyramidal iron Lee, Yunho; Mankad, Neal P.; Peters, Jonas C. Nature Chemistry, Vol. 2, Issue 7 https://doi.org/10.1038/nchem.660	journal	May 2010
Silylation of Iron-Bound Carbon Monoxide Affords a Terminal Fe Carbyne Lee, Yunho; Peters, Jonas C. Journal of the American Chemical Society, Vol. 133, Issue 12 https://doi.org/10.1021/ja109678y	journal	March 2011
Dinitrogen Activation at Iron and Cobalt Metallalumatranes Rudd, P. Alex; Planas, Nora; Bill, Eckhard European Journal of Inorganic Chemistry, Vol. 2013, Issue 22-23 https://doi.org/10.1002/ejic.201300272	journal	July 2013
Mössbauer Spectroscopy and Transition Metal Chemistry: Fundamentals and Applications Gütlich, Philipp; Bill, Eckhard; Trautwein, Alfred X. https://doi.org/10.1007/978-3-540-88428-6	book	January 2011
Electronic absorption and emission spectra of complexes containing dichromium, dimolybdenum, and ditungsten quadruple bonds Manning, Mark C.; Trogler, William C. Journal of the American Chemical Society, Vol. 105, Issue 16 https://doi.org/10.1021/ja00354a021	journal	August 1983
Chromium(II) and molybdenum(II) N,N-diethylcarbamato complexes from metal halides/carbon dioxide/diethylamine: crystal and molecular structure of the quadruply metal-metal-bonded Mo2(O2CNEt2)4 Belforte, Antonio; Belli Dell'Amico, Daniela; Calderazzo, Fausto Inorganic Chemistry, Vol. 32, Issue 11 https://doi.org/10.1021/ic00063a016	journal	May 1993
A Combined Spectroscopic and Computational Study of a High-Spin S = 7/2 Diiron Complex with a Short Iron–Iron Bond Zall, Christopher M.; Zherebetskyy, Danylo; Dzubak, Allison L. Inorganic Chemistry, Vol. 51, Issue 1 https://doi.org/10.1021/ic202384b	journal	December 2011
Metal−Metal Bonding and Structures of Metal String Complexes Cr ₃ (dpa) ₄ Cl ₂ , Cr ₃ (dpa) ₄ (NCS) ₂ , and [Cr ₃ (dpa) ₄ Cl ₂ ](PF ₆ ) from IR, Raman, and Surface-Enhanced Raman Spectra Hsiao, Chung-Jen; Lai, Szu-Hsueh; Chen, I-Chia The Journal of Physical Chemistry A, Vol. 112, Issue 51 https://doi.org/10.1021/jp8081326	journal	December 2008
Nature of Bonding in Complexes Containing “Supershort” Metal−Metal Bonds. Raman and Theoretical Study of M ₂ (dmp) ₄ [M = Cr (Natural Abundance Cr, ⁵⁰ Cr, and ⁵⁴ Cr) and Mo; dmp = 2,6-Dimethoxyphenyl] Da Re, Ryan E.; Eglin, Judith L.; Carlson, Christin N. Journal of the American Chemical Society, Vol. 132, Issue 6 https://doi.org/10.1021/ja9055504	journal	February 2010
A triad of homologous, air-stable compounds containing short, quadruple bonds between metal atoms of Group 6 Cotton, F. Albert; Fanwick, Phillip E.; Niswander, Ron H. Journal of the American Chemical Society, Vol. 100, Issue 15 https://doi.org/10.1021/ja00483a016	journal	July 1978
Molecular Structures, Vibrational Spectroscopy, and Normal-Mode Analysis of M ₂ (C⋮CR) ₄ (PMe ₃ ) ₄ Dimetallatetraynes. Observation of Strongly Mixed Metal−Metal and Metal−Ligand Vibrational Modes John, Kevin D.; Miskowski, Vincent M.; Vance, Michael A. Inorganic Chemistry, Vol. 37, Issue 26 https://doi.org/10.1021/ic980866u	journal	December 1998
The nature of the normal modes of [Mo2(CN)8]4− Clark, Robin J. H.; Firth, Steven; Sella, Andrea Journal of the Chemical Society, Dalton Transactions, Issue 17 https://doi.org/10.1039/b004186f	journal	January 2000
The molybdenum-molybdenum triple bond. 1. Hexakis(dimethylamido)dimolybdenum and some homologs: preparation, structure, and properties Chisholm, Malcolm H.; Cotton, F. Albert; Frenz, B. A. Journal of the American Chemical Society, Vol. 98, Issue 15 https://doi.org/10.1021/ja00431a024	journal	July 1976
The tungsten-tungsten triple bond. 1. Preparation, properties, and structural characterization of hexakis(dimethylamido)ditungsten(III) and some homologs Chisholm, Malcolm H.; Cotton, F. Albert; Extine, Michael Journal of the American Chemical Society, Vol. 98, Issue 15 https://doi.org/10.1021/ja00431a025	journal	July 1976
Density functional theory for transition metals and transition metal chemistry Cramer, Christopher J.; Truhlar, Donald G. Physical Chemistry Chemical Physics, Vol. 11, Issue 46 https://doi.org/10.1039/b907148b	journal	January 2009
Multireference Configuration Interaction Calculations on Cr ₂ : Passing the One Billion Limit in MRCI/MRACPF Calculations Dachsel, Holger; Harrison, Robert J.; Dixon, David A. The Journal of Physical Chemistry A, Vol. 103, Issue 1 https://doi.org/10.1021/jp982648s	journal	January 1999
Dichromium revisited: a resonance Raman study of Cr2 isolated in argon, krypton and xenon matrixes Moskovits, M.; Limm, W.; Mejean, T. The Journal of Physical Chemistry, Vol. 89, Issue 18 https://doi.org/10.1021/j100264a024	journal	August 1985

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Metal-Metal Single Bonds with the Magnetic Anisotropy of Quadruple Bonds: A Systematic Series of Heterobimetallic Bismuth(II)-Rhodium(II) Formamidinate Complexes Sunderland, Travis L.; Berry, John F. Chemistry - A European Journal, Vol. 22, Issue 51 https://doi.org/10.1002/chem.201604007	journal	November 2016
An Unsaturated Four-Coordinate Dimethyl Dimolybdenum Complex with a Molybdenum-Molybdenum Quadruple Bond Curado, Natalia; Carrasco, Mario; Campos, Jesús Chemistry - A European Journal, Vol. 23, Issue 1 https://doi.org/10.1002/chem.201604618	journal	December 2016
Synthesis of the Unsaturated [MMoCp(µ-PR 2 )(CO) 5 ] - Anions (M = Mn, R = Ph; M = Re, R = Cy): Versatile Precursors of Heterometallic Complexes : Synthesis of the Unsaturated [MMoCp(µ-PR Alvarez, M. Angeles; García, M. Esther; García-Vivó, Daniel European Journal of Inorganic Chemistry, Vol. 2017, Issue 9 https://doi.org/10.1002/ejic.201700040	journal	March 2017
Structure and dynamic NMR behavior of rhodium complexes supported by Lewis acidic group 13 metallatranes Moore, James T.; Smith, Nicholas E.; Lu, Connie C. Dalton Transactions, Vol. 46, Issue 17 https://doi.org/10.1039/c6dt04769f	journal	January 2017
How to understand very weak Cr–Cr double bonds and negative spin populations in trinuclear Cr complexes: theoretical insight Nakagaki, Masayuki; Nakatani, Naoki; Sakaki, Shigeyoshi Physical Chemistry Chemical Physics, Vol. 21, Issue 41 https://doi.org/10.1039/c9cp03645h	journal	January 2019
Kinetic versus thermodynamic metalation enables synthesis of isostructural homo- and heterometallic trinuclear clusters Hyun, Sung-Min; Upadhyay, Apoorva; Das, Anuvab Chemical Communications, Vol. 56, Issue 44 https://doi.org/10.1039/d0cc02346a	journal	January 2020
An iron ketimide single-molecule magnet [Fe ₄ (NCPh ₂ ) ₆ ] with suppressed through-barrier relaxation Cook, Andrew W.; Bocarsly, Joshua D.; Lewis, Richard A. Chemical Science, Vol. 11, Issue 18 https://doi.org/10.1039/d0sc01578d	journal	January 2020
The bond length and bond energy of gaseous CrW Matthew, Daniel J.; Oh, Sang Hoon; Sevy, Andrew The Journal of Chemical Physics, Vol. 144, Issue 21 https://doi.org/10.1063/1.4952453	journal	June 2016
Relevance of effective bond orders in heterodiatomic molecules and role of the spin-orbit coupling in the $At X$ $(X = At - F)$ series Pech, Cecilia Gomez; Haase, Pi A. B.; Galland, Nicolas Physical Review A, Vol. 100, Issue 3 https://doi.org/10.1103/physreva.100.032518	journal	September 2019
Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes Moore, James T.; Chatterjee, Sudipta; Tarrago, Maxime Inorganic Chemistry, Vol. 58, Issue 9 https://doi.org/10.1021/acs.inorgchem.9b00442	journal	April 2019
δ and φ back-donation in AnIV metallacycles Kelley, Morgan P.; Popov, Ivan A.; Jung, Julie Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15197-w	journal	March 2020

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CCDC 1051668: Experimental Crystal Structure Determination Eisenhart, Reed J.; Planas, Nora; Rudd, P. Alex https://doi.org/10.5517/cc149bsk The current record is supplemented by this dataset	dataset	January 2015
CCDC 1051669: Experimental Crystal Structure Determination Eisenhart, Reed J.; Planas, Nora; Rudd, P. Alex https://doi.org/10.5517/cc149btl The current record is supplemented by this dataset	dataset	January 2015
CCDC 1051670: Experimental Crystal Structure Determination Eisenhart, Reed J.; Planas, Nora; Rudd, P. Alex https://doi.org/10.5517/cc149bvm The current record is supplemented by this dataset	dataset	January 2015
CCDC 1051671: Experimental Crystal Structure Determination Eisenhart, Reed J.; Planas, Nora; Rudd, P. Alex https://doi.org/10.5517/cc149bwn The current record is supplemented by this dataset	dataset	January 2015
CCDC 1051672: Experimental Crystal Structure Determination Eisenhart, Reed J.; Planas, Nora; Rudd, P. Alex https://doi.org/10.5517/cc149bxp The current record is supplemented by this dataset	dataset	January 2015