Metal–Ligand Covalency in the Valence Excited States of Metal Dithiolenes Revealed by S 1s3p Resonant Inelastic X-ray Scattering

Larsen, Christopher B.; Ledbetter, Kathryn; Nascimento, Daniel R.; Biasin, Elisa; Qureshi, Muhammad; Nowak, Stanisław H.; Sokaras, Dimosthenis; Govind, Niranjan; Cordones, Amy A.

doi:10.1021/jacs.4c11667

Metal–Ligand Covalency in the Valence Excited States of Metal Dithiolenes Revealed by S 1s3p Resonant Inelastic X-ray Scattering

Journal Article · Tue Oct 08 04:00:00 EDT 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c11667· OSTI ID:2472473

^[1]; ^[1]; ^[2]; Biasin, Elisa ^[3]; Qureshi, Muhammad ^[4]; Nowak, Stanisław H. ^[4]; Sokaras, Dimosthenis ^[4]; ^[5]; ^[1]

Stanford PULSE Institute, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025, United States
Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
Stanford PULSE Institute, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025, United States, Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
SSRL, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States, Department of Chemistry, University of Washington, Seattle, Washington 98195, United States

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Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI ID:: 2472473

Alternate ID(s):: OSTI ID: 2522692
OSTI ID: 2472521
OSTI ID: 2589217

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society; ISSN 0002-7863

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (65)

Description of the Ground-State Covalencies of the Bis(dithiolato) Transition-Metal Complexes from X-ray Absorption Spectroscopy and Time-Dependent Density-Functional Calculations Ray, Kallol; DeBeer George, Serena; Solomon, Edward I. Chemistry - A European Journal, Vol. 13, Issue 10 https://doi.org/10.1002/chem.200601425	journal	March 2007
Metal–thiolate bonds in bioinorganic chemistry Solomon, Edward I.; Gorelsky, Serge I.; Dey, Abhishek Journal of Computational Chemistry, Vol. 27, Issue 12 https://doi.org/10.1002/jcc.20451	journal	January 2006
Multiwfn: A multifunctional wavefunction analyzer Lu, Tian; Chen, Feiwu Journal of Computational Chemistry, Vol. 33, Issue 5 https://doi.org/10.1002/jcc.22885	journal	December 2011
An evaluation of the performance of diffuse function-augmented basis sets for second row elements, Na-Cl: Diffuse Function-Augmented Basis Sets Spitznagel, Günther W.; Clark, Timothy; von Ragué Schleyer, Paul Journal of Computational Chemistry, Vol. 8, Issue 8 https://doi.org/10.1002/jcc.540080807	journal	December 1987
Segmented contracted basis sets for atoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q) Noro, Takeshi; Sekiya, Masahiro; Koga, Toshikatsu Theoretical Chemistry Accounts, Vol. 131, Issue 2 https://doi.org/10.1007/s00214-012-1124-z	journal	February 2012
Chemical effects in X-ray Kα and Kβ emission spectra of sulfur in organic compounds Yasuda, Seiji; Kakiyama, Hitoo Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 35, Issue 5 https://doi.org/10.1016/0584-8539(79)80164-6	journal	January 1979
Time dependent density functional theory of core electrons excitations Stener, M.; Fronzoni, G.; de Simone, M. Chemical Physics Letters, Vol. 373, Issue 1-2 https://doi.org/10.1016/S0009-2614(03)00543-8	journal	May 2003
Time-dependent density functional theory within the Tamm–Dancoff approximation Hirata, So; Head-Gordon, Martin Chemical Physics Letters, Vol. 314, Issue 3-4 https://doi.org/10.1016/S0009-2614(99)01149-5	journal	December 1999
Homogeneous catalysis with transition metal complexes containing sulfur ligands Bayón, J. Carles; Claver, Carmen; Masdeu-Bultó, Anna M. Coordination Chemistry Reviews, Vol. 193-195 https://doi.org/10.1016/S0010-8545(99)00169-1	journal	October 1999
Dithiolene radicals: Sulfur K-edge X-ray absorption spectroscopy and Harry's intuition Sproules, Stephen; Wieghardt, Karl Coordination Chemistry Reviews, Vol. 255, Issue 7-8 https://doi.org/10.1016/j.ccr.2010.12.006	journal	April 2011
Electronic structure of [Ni(II)S4] complexes from S K-edge X-ray absorption spectroscopy Queen, Matt S.; Towey, Bradley D.; Murray, Kevin A. Coordination Chemistry Reviews, Vol. 257, Issue 2 https://doi.org/10.1016/j.ccr.2012.07.020	journal	January 2013
Metal dithiolene complexes in olefin addition and purification, small molecule adsorption, H2 evolution and CO2 reduction Pitchaimani, Jayaraman; Ni, Shao-Fei; Dang, Li Coordination Chemistry Reviews, Vol. 420 https://doi.org/10.1016/j.ccr.2020.213398	journal	October 2020
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations Valiev, M.; Bylaska, E. J.; Govind, N. Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489 https://doi.org/10.1016/j.cpc.2010.04.018	journal	September 2010
Electronic Structure of Sulfur Studied by X-ray Absorption and Emission Spectroscopy Alonso Mori, R.; Paris, E.; Giuli, G. Analytical Chemistry, Vol. 81, Issue 15 https://doi.org/10.1021/ac900970z	journal	August 2009
Bio-inspired, Multifunctional Metal–Thiolate Motif: From Electron Transfer to Sulfur Reactivity and Small-Molecule Activation Gennari, Marcello; Duboc, Carole Accounts of Chemical Research, Vol. 53, Issue 11 https://doi.org/10.1021/acs.accounts.0c00555	journal	October 2020
Cooperative Catalysis at Metal–Sulfur Bonds Omann, Lukas; Königs, C. David F.; Klare, Hendrik F. T. Accounts of Chemical Research, Vol. 50, Issue 5 https://doi.org/10.1021/acs.accounts.7b00089	journal	April 2017
Metal–Sulfur Compounds in N ₂ Reduction and Nitrogenase-Related Chemistry Tanifuji, Kazuki; Ohki, Yasuhiro Chemical Reviews, Vol. 120, Issue 12 https://doi.org/10.1021/acs.chemrev.9b00544	journal	May 2020
From the Free Ligand to the Transition Metal Complex: FeEDTA^– Formation Seen at Ligand K-Edges Eckert, Sebastian; Mascarenhas, Eric J.; Mitzner, Rolf Inorganic Chemistry, Vol. 61, Issue 27 https://doi.org/10.1021/acs.inorgchem.2c00789	journal	June 2022
Uncovering the 3d and 4d Electronic Interactions in Solvated Ru Complexes with 2p3d Resonant Inelastic X-ray Scattering Poulter, Benjamin I.; Biasin, Elisa; Nowak, Stanisław H. Inorganic Chemistry, Vol. 62, Issue 25 https://doi.org/10.1021/acs.inorgchem.3c00919	journal	June 2023
Probing the Electron Accepting Orbitals of Ni-Centered Hydrogen Evolution Catalysts with Noninnocent Ligands by Ni L-Edge and S K-Edge X-ray Absorption Koroidov, Sergey; Hong, Kiryong; Kjaer, Kasper S. Inorganic Chemistry, Vol. 57, Issue 21 https://doi.org/10.1021/acs.inorgchem.8b01497	journal	October 2018
Resonant Inelastic X-ray Scattering Calculations of Transition Metal Complexes Within a Simplified Time-Dependent Density Functional Theory Framework Nascimento, Daniel R.; Biasin, Elisa; Poulter, Benjamin I. Journal of Chemical Theory and Computation, Vol. 17, Issue 5 https://doi.org/10.1021/acs.jctc.1c00144	journal	April 2021
Probing Sulfur Chemical and Electronic Structure with Experimental Observation and Quantitative Theoretical Prediction of Kα and Valence-to-Core Kβ X-ray Emission Spectroscopy Holden, William M.; Jahrman, Evan P.; Govind, Niranjan The Journal of Physical Chemistry A, Vol. 124, Issue 26 https://doi.org/10.1021/acs.jpca.0c04195	journal	June 2020
Sulfur X-ray Absorption and Emission Spectroscopy of Organic Sulfones Vogt, Linda I.; Cotelesage, Julien J. H.; Dolgova, Natalia V. The Journal of Physical Chemistry A, Vol. 127, Issue 16 https://doi.org/10.1021/acs.jpca.2c08647	journal	March 2023
Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives Kunnus, Kristjan; Zhang, Wenkai; Delcey, Mickaël G. The Journal of Physical Chemistry B, Vol. 120, Issue 29 https://doi.org/10.1021/acs.jpcb.6b04751	journal	July 2016
Operando Resonant Inelastic X-ray Scattering: An Appropriate Tool to Characterize Sulfur in Li–S Batteries Kavčič, M.; Bučar, K.; Petric, M. The Journal of Physical Chemistry C, Vol. 120, Issue 43 https://doi.org/10.1021/acs.jpcc.6b06705	journal	October 2016
Following Metal-to-Ligand Charge-Transfer Dynamics with Ligand and Spin Specificity Using Femtosecond Resonant Inelastic X-ray Scattering at the Nitrogen K-Edge Jay, Raphael M.; Eckert, Sebastian; Van Kuiken, Benjamin E. The Journal of Physical Chemistry Letters, Vol. 12, Issue 28 https://doi.org/10.1021/acs.jpclett.1c01401	journal	July 2021
Linear-Response and Real-Time Time-Dependent Density Functional Theory Studies of Core-Level Near-Edge X-Ray Absorption Lopata, K.; Van Kuiken, B. E.; Khalil, M. Journal of Chemical Theory and Computation, Vol. 8, Issue 9 https://doi.org/10.1021/ct3005613	journal	August 2012
Photoelectrochemical studies of maleonitriledithiolate complexes of nickel, palladium, platinum and copper Persaud, Lalchan; Langford, Cooper H. Inorganic Chemistry, Vol. 24, Issue 22 https://doi.org/10.1021/ic00216a018	journal	October 1985
Electronic Structure of Square Planar Bis(benzene-1,2-dithiolato)metal Complexes [M(L) ₂ ] ^z ^{( z = 2−, 1−, 0; M = Ni, Pd, Pt, Cu, Au): An Experimental, Density Functional, and Correlated ab Initio Study} Ray, Kallol; Weyhermüller, Thomas; Neese, Frank Inorganic Chemistry, Vol. 44, Issue 15 https://doi.org/10.1021/ic0507565	journal	July 2005
Sulfur-Metal Orbital Hybridization in Sulfur-Bearing Compounds Studied by X-ray Emission Spectroscopy Mori, R. Alonso; Paris, E.; Giuli, G. Inorganic Chemistry, Vol. 49, Issue 14 https://doi.org/10.1021/ic100304z	journal	July 2010
Noninnocence in Metal Complexes: A Dithiolene Dawn Eisenberg, Richard; Gray, Harry B. Inorganic Chemistry, Vol. 50, Issue 20 https://doi.org/10.1021/ic2011748	journal	October 2011
The Preparation and Characterization of Four-Coordinate Complexes Related by Electron-Transfer Reactions Davison, A.; Edelstein, N.; Holm, R. H. Inorganic Chemistry, Vol. 2, Issue 6 https://doi.org/10.1021/ic50010a031	journal	December 1963
The Electronic Structures of Square-Planar Metal Complexes. II. The Complexes of Maleonitriledithiolate with Copper(II), Nickel(II), Palladium(II), and Platinum(II) Billig, E.; Williams, Raymond; Bernal, I. Inorganic Chemistry, Vol. 3, Issue 5 https://doi.org/10.1021/ic50015a013	journal	May 1964
Pulsed ENDOR and ESEEM Study of [Bis(maleonitriledithiolato)nickel] ^- : An Investigation into the Ligand Electronic Structure Huyett, Jennifer E.; Choudhury, Suranjan B.; Eichhorn, David M. Inorganic Chemistry, Vol. 37, Issue 6 https://doi.org/10.1021/ic9703639	journal	March 1998
Relationship between the Dipole Strength of Ligand Pre-Edge Transitions and Metal−Ligand Covalency Neese, Frank; Hedman, Britt; Hodgson, Keith O. Inorganic Chemistry, Vol. 38, Issue 21 https://doi.org/10.1021/ic990461p	journal	October 1999
Electronic ground state of bis (maleonitrile-dithiolene)nickel monoanion. Sulfur-33 hyperfine interaction Schmitt, Richard D.; Maki, August H. Journal of the American Chemical Society, Vol. 90, Issue 9 https://doi.org/10.1021/ja01011a014	journal	April 1968
The Electronic Structures of Square-Planar Metal Complexes. V. Spectral Properties of the Maleonitriledithiolate Complexes of Nickel, Palladium, and Platinum Shupack, S. I.; Billig, E.; Clark, R. J. H. Journal of the American Chemical Society, Vol. 86, Issue 21 https://doi.org/10.1021/ja01075a016	journal	November 1964
Description of the Ground State Wave Functions of Ni Dithiolenes Using Sulfur K-edge X-ray Absorption Spectroscopy Szilagyi, Robert K.; Lim, Booyong S.; Glaser, Thorsten Journal of the American Chemical Society, Vol. 125, Issue 30 https://doi.org/10.1021/ja029806k	journal	July 2003
Sulfur K-Edge X-ray Absorption Spectroscopy as a Probe of Ligand−Metal Bond Covalency: Metal vs Ligand Oxidation in Copper and Nickel Dithiolene Complexes Sarangi, Ritimukta; DeBeer George, Serena; Rudd, Deanne Jackson Journal of the American Chemical Society, Vol. 129, Issue 8 https://doi.org/10.1021/ja0665949	journal	February 2007
Sulfur K-Edge X-ray Absorption Spectroscopy and Density Functional Calculations on Mo(IV) and Mo(VI)═O Bis-dithiolenes: Insights into the Mechanism of Oxo Transfer in DMSO Reductase and Related Functional Analogues Tenderholt, Adam L.; Wang, Jun-Jieh; Szilagyi, Robert K. Journal of the American Chemical Society, Vol. 132, Issue 24 https://doi.org/10.1021/ja910369c	journal	May 2010
Reduction of Electron Repulsion in Highly Covalent Fe-Amido Complexes Counteracts the Impact of a Weak Ligand Field on Excited-State Ordering Larsen, Christopher B.; Braun, Jason D.; Lozada, Issiah B. Journal of the American Chemical Society, Vol. 143, Issue 49 https://doi.org/10.1021/jacs.1c06429	journal	December 2021
Illuminating Ligand Field Contributions to Molecular Qubit Spin Relaxation via T₁ Anisotropy Kazmierczak, Nathanael P.; Hadt, Ryan G. Journal of the American Chemical Society, Vol. 144, Issue 45 https://doi.org/10.1021/jacs.2c08729	journal	November 2022
Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study Engel, Nicholas; Bokarev, Sergey I.; Suljoti, Edlira The Journal of Physical Chemistry B, Vol. 118, Issue 6 https://doi.org/10.1021/jp411782y	journal	January 2014
Resonant Inelastic X-ray Scattering of Molybdenum Oxides and Sulfides Thomas, Rowena; Kas, Josh; Glatzel, Pieter The Journal of Physical Chemistry C https://doi.org/10.1021/jp509376q	journal	January 2015
The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe( ii ) complexes Jay, Raphael M.; Eckert, Sebastian; Fondell, Mattis Physical Chemistry Chemical Physics, Vol. 20, Issue 44 https://doi.org/10.1039/C8CP04341H	journal	January 2018
Recent advances in the mechanisms of the hydrogen evolution reaction by non-innocent sulfur-coordinating metal complexes Drosou, Maria; Kamatsos, Fotios; Mitsopoulou, Christiana A. Inorganic Chemistry Frontiers, Vol. 7, Issue 1 https://doi.org/10.1039/C9QI01113G	journal	January 2020
Sulfur Kβ X-ray emission spectroscopy: comparison with sulfur K-edge X-ray absorption spectroscopy for speciation of organosulfur compounds Qureshi, Muhammad; Nowak, Stanisław H.; Vogt, Linda I. Physical Chemistry Chemical Physics, Vol. 23, Issue 8 https://doi.org/10.1039/D0CP05323F	journal	January 2021
Revealing the bonding of solvated Ru complexes with valence-to-core resonant inelastic X-ray scattering Biasin, Elisa; Nascimento, Daniel R.; Poulter, Benjamin I. Chemical Science, Vol. 12, Issue 10 https://doi.org/10.1039/D0SC06227H	journal	January 2021
Unsupervised machine learning for unbiased chemical classification in X-ray absorption spectroscopy and X-ray emission spectroscopy Tetef, Samantha; Govind, Niranjan; Seidler, Gerald T. Physical Chemistry Chemical Physics, Vol. 23, Issue 41 https://doi.org/10.1039/D1CP02903G	journal	January 2021
Computational approaches for XANES, VtC-XES, and RIXS using linear-response time-dependent density functional theory based methods Nascimento, Daniel R.; Govind, Niranjan Physical Chemistry Chemical Physics, Vol. 24, Issue 24 https://doi.org/10.1039/D2CP01132H	journal	January 2022
Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands Ray, Kallol; Petrenko, Taras; Wieghardt, Karl Dalton Transactions, Issue 16 https://doi.org/10.1039/b700096k	journal	January 2007
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions Krishnan, R.; Binkley, J. S.; Seeger, R. The Journal of Chemical Physics, Vol. 72, Issue 1 https://doi.org/10.1063/1.438955	journal	January 1980
Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 McLean, A. D.; Chandler, G. S. The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648 https://doi.org/10.1063/1.438980	journal	May 1980
Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements Francl, Michelle M.; Pietro, William J.; Hehre, Warren J. The Journal of Chemical Physics, Vol. 77, Issue 7, p. 3654-3665 https://doi.org/10.1063/1.444267	journal	October 1982
Structural and dynamical properties of chlorinated hydrocarbons studied with resonant inelastic x-ray scattering Bohinc, R.; Žitnik, M.; Bučar, K. The Journal of Chemical Physics, Vol. 144, Issue 13 https://doi.org/10.1063/1.4945402	journal	April 2016
A versatile Johansson-type tender x-ray emission spectrometer Nowak, S. H.; Armenta, R.; Schwartz, C. P. Review of Scientific Instruments, Vol. 91, Issue 3 https://doi.org/10.1063/1.5121853	journal	March 2020
NWChem: Past, present, and future Aprà, E.; Bylaska, E. J.; de Jong, W. A. The Journal of Chemical Physics, Vol. 152, Issue 18 https://doi.org/10.1063/5.0004997	journal	May 2020
5f covalency from x-ray resonant Raman spectroscopy Tobin, J. G.; Nowak, S.; Yu, S-W Journal of Physics: Condensed Matter, Vol. 34, Issue 50 https://doi.org/10.1088/1361-648X/ac9bbd	journal	October 2022
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Resonant inelastic x-ray scattering spectra for electrons in solids Kotani, Akio; Shin, Shik Reviews of Modern Physics, Vol. 73, Issue 1 https://doi.org/10.1103/RevModPhys.73.203	journal	February 2001
PINK: a tender X-ray beamline for X-ray emission spectroscopy Peredkov, Sergey; Pereira, Nilson; Grötzsch, Daniel Journal of Synchrotron Radiation, Vol. 31, Issue 3 https://doi.org/10.1107/S1600577524002200	journal	April 2024
Electron Spectroscopy for Atoms, Molecules, and Condensed Matter Siegbahn, K. Science, Vol. 217, Issue 4555 https://doi.org/10.1126/science.217.4555.111	journal	July 1982
Capturing Atom-Specific Electronic Structural Dynamics of Transition-Metal Complexes with Ultrafast Soft X-Ray Spectroscopy Jay, Raphael M.; Kunnus, Kristjan; Wernet, Philippe Annual Review of Physical Chemistry, Vol. 73, Issue 1 https://doi.org/10.1146/annurev-physchem-082820-020236	journal	April 2022
Transition metal sulfur chemistry and its relevance to molybdenum and tungsten enzymes Stiefel, E. I. Pure and Applied Chemistry, Vol. 70, Issue 4 https://doi.org/10.1351/pac199870040889	journal	January 1998

Metal–Ligand Covalency in the Valence Excited States of Metal Dithiolenes Revealed by S 1s3p Resonant Inelastic X-ray Scattering

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Metal–Ligand Covalency in the Valence Excited States of Metal Dithiolenes Revealed by S 1s3p Resonant Inelastic X-ray Scattering

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