Abstract
Knowledge of the electronic structure of transition-metal complexes is increasingly being obtained through joint efforts by theory and experiments. Here, we describe a variety of examples where spectroscopy is being used to determine, e.g., the oxidation state, spin state, or coordination environment around redox-active metal ions such as iron , manganese , or nickel . Both enzymatic and biomimetic systems are included, from the literature and from our own laboratories. It is shown that the combined efforts of wet and dry laboratories lead to a more profound understanding, and allows for systematic exploration of coordinate chemistry around the central metal atom.
Keywords
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Swart M, Costas M (eds) (2015) Spin states in biochemistry and inorganic chemistry: influence on structure and reactivity. Wiley, Oxford. https://doi.org/10.1002/9781118898277
Que Jr L (2000) Physical methods in bioinorganic chemistry. University Science Books
Crichton R, Louro R (2013) Practical approaches to biological inorganic chemistry. Elsevier
Ray K, Duboc C (2018) ECOSTBio: explicit control over spin states in technology and biochemistry. Chem Eur J 24:5003–5005. https://doi.org/10.1002/chem.201801041
Bergeler M, Stiebritz MT, Reiher M (2013) Structure–property relationships of Fe4S4 clusters. ChemPlusChem 78:1082–1098
Carvalho ATP, Swart M (2014) Electronic structure investigation and parameterization of biologically relevant iron-sulfur clusters. J Chem Inf Model 54:613–620
Sharma S, Sivalingam K, Neese F, Chan GK-L (2014) Low-energy spectrum of iron–sulfur clusters directly from many-particle quantum mechanics. Nat Chem 6:927–933. https://doi.org/10.1038/nchem.2041
Kim J, Rees DC (1992) Structural models for the metal centers in the nitrogenase molybdenum-iron protein. Science 257:1677–1682. https://doi.org/10.1126/science.1529354
Einsle O, Tezcan FA, Andrade SLA, Schmid B, Yoshida M, Howard JB, Rees DC (2002) Nitrogenase MoFe-protein at 1.16 Å resolution: a central ligand in the FeMo-cofactor. Science 297:1696–1700. https://doi.org/10.1126/science.1073877
Ramaswamy S (2011) One atom makes all the difference. Science 334:914–915. https://doi.org/10.1126/science.1215283
Spatzal T et al (2011) Evidence for interstitial carbon in nitrogenase FeMo cofactor. Science 334:940–940. https://doi.org/10.1126/science.1214025
Yang T-C, Maeser NK, Laryukhin M, Lee H-I, Dean DR, Seefeldt LC, Hoffman BM (2005) The interstitial atom of the nitrogenase FeMo-cofactor: ENDOR and ESEEM evidence that it is not a nitrogen. J Am Chem Soc 127:12804–12805. https://doi.org/10.1021/ja0552489
Lancaster KM et al (2011) X-Ray emission spectroscopy evidences a central carbon in the nitrogenase iron-molybdenum cofactor. Science 334:974–977. https://doi.org/10.1126/science.1206445
Bjornsson R et al (2014) Identification of a spin-coupled Mo(III) in the nitrogenase iron–molybdenum cofactor. Chem Sci 5:3096–3103. https://doi.org/10.1039/c4sc00337c
Sippel D et al (2018) A bound reaction intermediate sheds light on the mechanism of nitrogenase. Science 359:1484–1489. https://doi.org/10.1126/science.aar2765
Cao L, Ryde U (2018) Influence of the protein and DFT method on the broken-symmetry and spin states in nitrogenase. Int J Quantum Chem 118:e25627. https://doi.org/10.1002/qua.25627
Cao L, Caldararu O, Ryde U (2017) Protonation states of homocitrate and nearby residues in nitrogenase studied by computational methods and quantum refinement. J Phys Chem B 121:8242–8262. https://doi.org/10.1021/acs.jpcb.7b02714
Siegbahn PEM (2018) A major structural change of the homocitrate ligand of probable importance for the nitrogenase mechanism. Inorg Chem 57:1090–1095. https://doi.org/10.1021/acs.inorgchem.7b02493
Siegbahn PEM (2016) Model calculations suggest that the central carbon in the femo-cofactor of nitrogenase becomes protonated in the process of nitrogen fixation. J Am Chem Soc 138:10485–10495. https://doi.org/10.1021/jacs.6b03846
Siegbahn PEM (2018) Is there computational support for an unprotonated carbon in the E4 state of nitrogenase? J Comput Chem 39:743–747. https://doi.org/10.1002/jcc.25145
Dau H, Iuzzolino L, Dittmer J (2001) The tetra-manganese complex of photosystem II during its redox cycle—X-ray absorption results and mechanistic implications. BBA-Bioenergetics 1503:24–39. https://doi.org/10.1016/s0005-2728(00)00230-9
Krewald V et al (2015) Metal oxidation states in biological water splitting. Chem Sci 6:1676–1695
Rohde JU et al (2003) Crystallographic and spectroscopic characterization of a nonheme Fe(IV)-O complex. Science 299:1037–1039. https://doi.org/10.1126/science.299.5609.1037
Fukuzumi S, Morimoto Y, Kotani H, Naumov P, Lee Y-M, Nam W (2010) Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer. Nat Chem 2:756–759. https://doi.org/10.1038/nchem.731
McDonald AR, Que Jr L (2013) High-valent nonheme iron-oxo complexes: synthesis, structure, and spectroscopy. Coord Chem Rev 257:414–428. https://doi.org/10.1016/j.ccr.2012.08.002
Swart M (2013) A change in oxidation state of iron: scandium is not innocent. Chem Commun 49:6650–6652. https://doi.org/10.1039/C3CC42200C
Swart M (2008) Accurate spin-state energies for iron complexes. J Chem Theory Comp 4:2057–2066
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximations made simple. Phys Rev Lett 77:3865–3868
Grimme S (2006) Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comput Chem 27:1787–1799
Swart M, Solà M, Bickelhaupt FM (2009) A new all-round DFT functional based on spin states and SN2 barriers. J Chem Phys 131:094103
Han W-G, Liu T, Lovell T, Noodleman L (2006) DFT calculations of 57Fe Mössbaurer isomer shifts and quadrupole splittings for iron complexes in polar dielectric media: applications to methane monooxygenase and ribonucleotide reductase. J Comput Chem 27:1292–1306
Güell M, Solà M, Swart M (2010) Spin-state splittings of iron(II) complexes with trispyrazolyl ligands. Polyhedron 29:84–93. https://doi.org/10.1016/j.poly.2009.06.006
MacBeth CE et al (2004) Utilization of hydrogen bonds to stabilize M-O(H) units: synthesis and properties of monomeric iron and manganese complexes with terminal oxo and hydroxo ligands. J Am Chem Soc 126:2556–2567. https://doi.org/10.1021/ja0305151
Cho J et al (2011) Structure and reactivity of a mononuclear non-haem iron(III)–peroxo complex. Nature 478:502–505
Swart M, Gruden M (2016) Spinning around in transition-metal chemistry. Acc Chem Res 49:2690–2697. https://doi.org/10.1021/acs.accounts.6b00271
Zhou A, Kleespies ST, Van Heuvelen KM, Que Jr L (2015) Characterization of a heterobimetallic nonheme Fe(III)–O–Cr(III) species formed by O2 activation. Chem Commun 51:14326–14329. https://doi.org/10.1039/c5cc05931c
Prakash J, Rohde GT, Meier KK, Münck E, Que Jr L (2015) Upside down! Crystallographic and spectroscopic characterization of an [FeIV(Osyn)(TMC)]2+ complex. Inorg Chem 54:11055–11057. https://doi.org/10.1021/acs.inorgchem.5b02011
Ray K, England J, Fiedler AT, Martinho M, Münck E, Que Jr L (2008) An inverted and more oxidizing isomer of [Fe(IV)(O)(tmc)(NCCH3)]2+. Angew Chem Int Ed 47:8068–8071. https://doi.org/10.1002/anie.200802219
Zhou A et al (2017) The two faces of tetramethylcyclam in iron chemistry: distinct Fe−O−M complexes derived from [FeIV(Oanti/syn)(TMC)]2+ isomers. Inorg Chem 56:518–527. https://doi.org/10.1021/acs.inorgchem.6b02417
Padamati SK et al (2017) Transient formation and reactivity of a high-valent nickel(IV) oxido complex. J Am Chem Soc 139:8718–8724. https://doi.org/10.1021/jacs.7b04158
Wieghardt K et al (1988) Synthesis, crystal structures, reactivity, and magnetochemistry of a series of binuclear complexes of manganese(II), -(III), and -(IV) of biological relevance. The crystal structure of [L′MnIV(m-O)3MnIVL′](PF6)2·H2O containing an unprecedented short Mn···Mn distance of 2.296 Å. J Am Chem Soc 110:7398–7411. https://doi.org/10.1021/ja00230a021
Neubold P, Della Vedova BSPC, Wieghardt K, Nuber B, Weiss J (1990) Novel cofacial bioctahedral complexes of ruthenium: syntheses and properties of the mixed-valence species [LRu2.5(.mu.-X)3Ru2.5L]2 + (X = Cl, Br, I, OH). Crystal structures of [LRu2.5(.mu.-OH)3Ru2.5L](PF6)2.cntdot.H2O and [LRuIV(.mu.-O)3RuIVL](PF6)2.cntdot.H2O (L = 1,4,7-trimethyl-1,4,7-triazacyclononane). Inorg Chem 29:3353–3363. https://doi.org/10.1021/ic00343a020
Rohde J-U et al. (2004) Structural insights into nonheme alkylperoxoiron(III) and oxoiron(IV) intermediates by X-ray absorption spectroscopy. J Am Chem Soc 126:16750–16761. https://doi.org/10.1021/ja047667w
Pirovano P, Farquhar E, Swart M, Fitzpatrick AJ, Morgan GG, McDonald AR (2015) Characterization and reactivity of a terminal nickel(III)-oxygen adduct. Chem Eur J 21:3785–3790. https://doi.org/10.1002/chem.201406485
Pirovano P, Farquhar ER, Swart M, McDonald AR (2016) Tuning the reactivity of terminal nickel(III)–oxygen adducts for C–H bond activation. J Am Chem Soc 138:14362–14370. https://doi.org/10.1021/jacs.6b08406
Gatteschi D, Sessoli R, Villain J (2006) Molecular nanomagnets. Oxford University Press, New-York
Mannini M et al (2009) Magnetic memory of a single-molecule quantum magnet wired to a gold surface. Nat Mater 8:194–197. https://doi.org/10.1038/nmat2374
Bogani L, Wernsdorfer W (2008) Molecular spintronics using single-molecule magnets. Nat Mater 7:179–186. https://doi.org/10.1038/nmat2133
Craig GA, Murrie M (2015) 3d single-ion magnets. Chem Soc Rev 44:2135–2142. https://doi.org/10.1039/c4cs00439f
Frost JM, Harriman KLM, Murugesu M (2016) The rise of 3-d single-ion magnets in molecular magnetism: towards materials from molecules? Chem Sci 7:2470–2491. https://doi.org/10.1039/c5sc03224e
Waldmann O (2007) A criterion for the anisotropy barrier in single-molecule magnets. Inorg Chem 46:10035–10037. https://doi.org/10.1021/ic701365t
Neese F, Pantazis DA (2011) What is not required to make a single molecule magnet. Faraday Discuss 148:229–238. https://doi.org/10.1039/C005256F
Duboc C, Gennari M (2015) Experimental techniques for determining spin states. In: Spin states in biochemistry and inorganic chemistry. Wiley, pp 59–83. https://doi.org/10.1002/9781118898277.ch4
Neese F (2006) Importance of direct spin-spin coupling and spin-flip excitations for the zero-field splitting of transition metal complexes: a case study. J Am Chem Soc 128:10213–10222. https://doi.org/10.1021/ja061798a
Sousa C, de Graaf C (2015) Ab initio wavefunction approaches to spin states. In: Spin states in biochemistry and inorganic chemistry. Wiley, pp 35–57. https://doi.org/10.1002/9781118898277.ch3
Daul CA, Zlatar M, Gruden-Pavlovic M, Swart M (2015) Application of density functional and density functional based ligand field theory to spin states. In: Spin states in biochemistry and inorganic chemistry. Wiley, pp 7–34. https://doi.org/10.1002/9781118898277.ch2
Pederson MR, Khanna SN (1999) Magnetic anisotropy barrier for spin tunneling in Mn12O12 molecules. Phys Rev B 60:9566–9572
Neese F, Solomon EI (1998) Calculation of zero-field splittings, g-values, and the relativistic nephelauxetic effect in transition metal complexes. Application to high-spin ferric complexes. Inorg Chem 37:6568–6582
Atanasov M, Daul CA, Rauzy C (2003) New insights into the effects of covalency on the ligand field parameters: a DFT study. Chem Phys Lett 367:737–746. https://doi.org/10.1016/s0009-2614(02)01762-1
Sessoli R, Gatteschi D, Caneschi A, Novak MA (1993) Magnetic bistability in a metal-ion cluster. Nature 365:141–143
Duboc C, Ganyushin D, Sivalingam K, Collomb M-N, Neese F (2010) Systematic theoretical study of the zero-field splitting in coordination complexes of Mn(III). Density functional theory versus multireference wave function approaches. J Phys Chem A 114:10750–10758. https://doi.org/10.1021/jp107823s
Duboc C (2016) Determination and prediction of the magnetic anisotropy of Mn ions. Chem Soc Rev 45:5834–5847. https://doi.org/10.1039/C5CS00898K
Zlatar M et al (2016) Origin of the zero-field splitting in mononuclear octahedral MnIV complexes: a combined experimental and theoretical investigation. Inorg Chem 55:1192–1201. https://doi.org/10.1021/acs.inorgchem.5b02368
Leto DF, Massie AA, Colmer HE, Jackson TA (2016) X-Band electron paramagnetic resonance comparison of mononuclear MnIV-oxo and MnIV-hydroxo complexes and quantum chemical investigation of MnIV zero-field splitting. Inorg Chem 55:3272–3282. https://doi.org/10.1021/acs.inorgchem.5b02309
Barra AL, Gatteschi D, Sessoli R, Abbati GL, Cornia A, Fabretti AC, Uytterhoeven MG (1997) Electronic structure of manganese(III) compounds from high-frequency EPR spectra. Angew Chem Int Ed 36:2329–2331
Goldberg DP, Telser J, Krzystek J, Montalban AG, Brunel L-C, Barrett AGM, Hoffman BM (1997) EPR spectra from “EPR-silent” species: high-field EPR spectroscopy of manganese(III) porphyrins. J Am Chem Soc 119:8722–8723. https://doi.org/10.1021/ja971169o
Duboc C, Collomb MN (2009) Multifrequency high-field EPR investigation of a mononuclear manganese(IV) complex. Chem Commun 2715–2717. https://doi.org/10.1039/b901185d
Brazzolotto D et al (2016) An experimental and theoretical investigation on pentacoordinated cobalt(III) complexes with an intermediate S = 1 spin state: how halide ligands affect their magnetic anisotropy. Chem Eur J 22:925–933. https://doi.org/10.1002/chem.201502997
Wang LK et al (2018) Experimental and theoretical identification of the origin of magnetic anisotropy in intermediate spin iron(III) complexes. Chem Eur J 24:5091–5094. https://doi.org/10.1002/chem.201705989
Duboc C, Phoeung T, Zein S, Pécaut J, Collomb MN, Neese F (2007) Origin of the zero-field splitting in mononuclear octahedral dihalide Mn-II complexes: an investigation by multifrequency high-field electron paramagnetic resonance and density functional theory. Inorg Chem 46:4905–4916. https://doi.org/10.1021/ic062384l
Ruamps R et al (2013) Giant Ising-type magnetic anisotropy in trigonal bipyramidal Ni(ii) complexes: experiment and theory. J Am Chem Soc 135:3017–3026. https://doi.org/10.1021/ja308146e
Gruden-Pavlovic M, Peric M, Zlatar M, Garcia-Fernandez P (2014) Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior. Chem Sci 5:1453–1462. https://doi.org/10.1039/c3sc52984c
Groom CR, Bruno IJ, Lightfoot MP, Ward SC (2016) The Cambridge structural database. Acta Cryst B 72:171–179. https://doi.org/10.1107/s2052520616003954
Rozell WJ, Wood JS (1977) Crystal and molecular-structures of 5-coordinate complexes [Ni(LCH3)2Cl3]ClO4 and [Cu(LCH3)2Cl3]ClO4, where L+CH3 = N-methyl-1,4-diazabicyclo[2.2.2]octonium ion. Inorg Chem 16:1827–1833. https://doi.org/10.1021/ic50174a001
Pritchard RG, Ali M, Munim A, Uddin A (2006) Effedcts d-orbital occupancy on the geometry of the trigonal-bipyramidal complexes (MCl3)-Cl-II(Hdabco)(dabco) (n), where M is Mn, Co, Ni or Cu and dabco is 1,4-diazabicyclo 2.2.2-octane. Acta Crystallogr Sect C Crystal Struct Commun 62:M507–M509. https://doi.org/10.1107/s0108270106037504
Marriott KER, Bhaskaran L, Wilson C, Medarde M, Ochsenbein ST, Hill S, Murrie M (2015) Pushing the limits of magnetic anisotropy in trigonal bipyramidal Ni(ii). Chem Sci 6:6823–6828. https://doi.org/10.1039/c5sc02854j
Nemec I, Herchel R, Svoboda I, Boca R, Travnicek Z (2015) Large and negative magnetic anisotropy in pentacoordinate mononuclear Ni(II) Schiff base complexes. Dalton Trans 44:9551–9560. https://doi.org/10.1039/c5dt00600g
Acknowledgements
The COST association action CM1305 ECOSTBio (STSM grant 34080), the European Research Council (ERC 279549, WRB), the labex arcane (ANR-11-LABX-003), MINECO (CTQ2014-59212-P, CTQ2015-70851-ERC, CTQ2017-87392-P, MS), GenCat (2014SGR1202, MS), FEDER (UNGI10-4E-801, MS), and the Serbian Ministry of Science (Grant No. 172035) are acknowledged for financial support.
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Gruden, M., Browne, W.R., Swart, M., Duboc, C. (2019). Computational Versus Experimental Spectroscopy for Transition Metals. In: Broclawik, E., Borowski, T., Radoń, M. (eds) Transition Metals in Coordination Environments. Challenges and Advances in Computational Chemistry and Physics, vol 29. Springer, Cham. https://doi.org/10.1007/978-3-030-11714-6_6
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