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Bis(imino)pyridine Iron Dinitrogen Compounds Revisited: Differences in Electronic Structure Between Four- and Five-Coordinate Derivatives.

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Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2012, 51, 6, 3770-3785
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    Bis(imino)pyridine Iron Dinitrogen Compounds Revisited: Differences in Electronic Structure Between Four- and Five-Coordinate Derivatives.
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    † Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States
    ‡ Cornell High Energy Synchrotron Source, Wilson Laboratory, Cornell University, Ithaca, New York 14853, United States
    § Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, United States
    ⊥ Max-Planck Institute for Bioinorganic Chemistry, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany
    *E-mail: [email protected] (P.J.C.).
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2012, 51, 6, 3770–3785
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    https://doi.org/10.1021/ic202750n
    Published March 6, 2012
    Copyright © 2012 American Chemical Society
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    Abstract

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    The electronic structures of the four- and five-coordinate aryl-substituted bis(imino)pyridine iron dinitrogen complexes, (iPrPDI)FeN2 and (iPrPDI)Fe(N2)2 (iPrPDI = 2,6-(2,6-iPr2–C6H3–N=CMe)2C5H3N), have been investigated by a combination of spectroscopic techniques (NMR, Mössbauer, X-ray Absorption, and X-ray Emission) and DFT calculations. Homologation of the imine methyl backbone to ethyl or isopropyl groups resulted in the preparation of the new bis(imino)pyridine iron dinitrogen complexes, (iPrRPDI)FeN2 (iPrRPDI = 2,6-(2,6-iPr2–C6H3–N=CR)2C5H3N; R = Et, iPr), that are exclusively four coordinate both in the solid state and in solution. The spectroscopic and computational data establish that the (iPrRPDI)FeN2 compounds are intermediate spin ferrous derivatives (SFe = 1) antiferromagnetically coupled to bis(imino)pyridine triplet diradical dianions (SPDI = 1). While this ground state description is identical to that previously reported for (iPrPDI)Fe(DMAP) (DMAP = 4-N,N-dimethylaminopyridine) and other four-coordinate iron compounds with principally σ-donating ligands, the d-orbital energetics determine the degree of coupling of the metal-chelate magnetic orbitals resulting in different NMR spectroscopic behavior. For (iPrRPDI)Fe(DMAP) and related compounds, this coupling is strong and results in temperature independent paramagnetism where a triplet excited state mixes with the singlet ground state via spin orbit coupling. In the (iPrRPDI)FeN2 family, one of the iron singly occupied molecular orbitals (SOMOs) is essentially dz2 in character resulting in poor overlap with the magnetic orbitals of the chelate, leading to thermal population of the triplet state and hence temperature dependent NMR behavior. The electronic structures of (iPrRPDI)FeN2 and (iPrPDI)Fe(DMAP) differ from (iPrPDI)Fe(N2)2, a highly covalent molecule with a redox noninnocent chelate that is best described as a resonance hybrid between iron(0) and iron(II) canonical forms as originally proposed in 2004.

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    Supporting Information

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    X-ray crystallographic data for (iPrEtPDI)FeN2 and (iPriPr PDI)FeN2 in cif format. SQUID, Mössbauer, IR, VT-XAS, XES fits, and calculated XAS and XES deconvolutions. This material is available free of charge via the Internet at http://pubs.acs.org.

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    60. Jonathan M. Darmon, S. Chantal E. Stieber, Kevin T. Sylvester, Ignacio Fernández, Emil Lobkovsky, Scott P. Semproni, Eckhard Bill, Karl Wieghardt, Serena DeBeer, and Paul J. Chirik . Oxidative Addition of Carbon–Carbon Bonds with a Redox-Active Bis(imino)pyridine Iron Complex. Journal of the American Chemical Society 2012, 134 (41) , 17125-17137. https://doi.org/10.1021/ja306526d
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    62. Zachary Thammavongsy, Takele Seda, Lev N. Zakharov, Werner Kaminsky, and John D. Gilbertson . Ligand-Based Reduction of CO2 and Release of CO on Iron(II). Inorganic Chemistry 2012, 51 (17) , 9168-9170. https://doi.org/10.1021/ic3015404
    63. Renyuan Pony Yu, Jonathan M. Darmon, Jordan M. Hoyt, Grant W. Margulieux, Zoë R. Turner, and Paul J. Chirik . High-Activity Iron Catalysts for the Hydrogenation of Hindered, Unfunctionalized Alkenes. ACS Catalysis 2012, 2 (8) , 1760-1764. https://doi.org/10.1021/cs300358m
    64. Scott P. Semproni, Carsten Milsmann, and Paul J. Chirik . Side-on Dinitrogen Complexes of Titanocenes with Disubstituted Cyclopentadienyl Ligands: Synthesis, Structure, and Spectroscopic Characterization. Organometallics 2012, 31 (9) , 3672-3682. https://doi.org/10.1021/om300156z
    65. Sven Strübbe, Michal Nowakowski, Roland Schoch, Matthias Bauer. High‐Resolution X‐ray Absorption and Emission Spectroscopy for Detailed Analysis of New CO 2 Methanation Catalysts. ChemPhysChem 2023, 24 (23) https://doi.org/10.1002/cphc.202300113
    66. Naved Akhtar, Manav Chauhan, Poorvi Gupta, Neha Antil, Kuntal Manna. A supported pyridylimine–cobalt catalyst for N -formylation of amines using CO 2. Dalton Transactions 2023, 52 (42) , 15384-15393. https://doi.org/10.1039/D3DT00058C
    67. Nicolas I. Regenauer, Hubert Wadepohl, Dragoş‐Adrian Roşca. Terminal N 2 Dissociation in [(PNN)Fe(N 2 )] 2 (μ‐N 2 ) Leads to Local Spin‐State Changes and Augmented Bridging N 2 Activation. Chemistry – A European Journal 2022, 28 (58) https://doi.org/10.1002/chem.202202172
    68. James E. T. Smith, Joonho Lee, Sandeep Sharma. Near-exact nuclear gradients of complete active space self-consistent field wave functions. The Journal of Chemical Physics 2022, 157 (9) https://doi.org/10.1063/5.0085515
    69. Daniela Sanchez Arana, Jaylan R. Billups, Bruno Donnadieu, Sidney E. Creutz. Synthesis and electronic structure of a series of first-row transition-metal pyrazine(diimine) complexes in two oxidation states. Journal of Coordination Chemistry 2022, 75 (11-14) , 1815-1840. https://doi.org/10.1080/00958972.2022.2115889
    70. Errikos Kounalis, Daniël L.J. Broere. Redox-Active Ligands in Organometallic Chemistry. 2022, 421-441. https://doi.org/10.1016/B978-0-12-820206-7.00028-7
    71. S. Chantal E. Stieber. Computational Methods in Organometallic Chemistry. 2022, 176-210. https://doi.org/10.1016/B978-0-12-820206-7.00099-8
    72. Michael L. Neidig, Nikki J. Bakas, Peter G.N. Neate, Jeffrey D. Sears. Metal-Carbon Bonds of Iron and Manganese. 2021, 82-122. https://doi.org/10.1016/B978-0-08-102688-5.00050-7
    73. David N. Stephens, Molly O’Hagan, Elliott Hulley, Michael T. Mock. Transition Metal Complexes for Dinitrogen Coordination and Activation. 2021, 363-409. https://doi.org/10.1016/B978-0-08-102688-5.00116-1
    74. Nicolas Mézailles. Reactivity and Structure of Complexes of Small Molecules: Dinitrogen. 2021, 875-958. https://doi.org/10.1016/B978-0-08-102688-5.00083-0
    75. William R. Buratto, Leslie J. Murray. Coordination Chemistry of Iron-Dinitrogen Complexes With Relevance to Biological N2 Fixation. 2021, 659-706. https://doi.org/10.1016/B978-0-12-409547-2.14822-X
    76. Jeongmin Cha, Hyunchul Kwon, Hayoung Song, Eunsung Lee. Dinitrogen activation by a penta-pyridyl molybdenum complex. Dalton Transactions 2020, 49 (37) , 12945-12949. https://doi.org/10.1039/D0DT02692A
    77. Evan P. Jahrman, William M. Holden, Niranjan Govind, Joshua J. Kas, Jatinkumar Rana, Louis F. J. Piper, Carrie Siu, M. Stanley Whittingham, Timothy T. Fister, Gerald T. Seidler. Valence-to-core X-ray emission spectroscopy of vanadium oxide and lithiated vanadyl phosphate materials. Journal of Materials Chemistry A 2020, 8 (32) , 16332-16344. https://doi.org/10.1039/D0TA03620J
    78. Nils Prinz, Leif Schwensow, Sven Wendholt, Andreas Jentys, Matthias Bauer, Wolfgang Kleist, Mirijam Zobel. Hard X-ray-based techniques for structural investigations of CO 2 methanation catalysts prepared by MOF decomposition. Nanoscale 2020, 12 (29) , 15800-15813. https://doi.org/10.1039/D0NR01750G
    79. Severine Rupp, Felix Plasser, Vera Krewald. Multi‐Tier Electronic Structure Analysis of Sita's Mo and W Complexes Capable of Thermal or Photochemical N 2 Splitting. European Journal of Inorganic Chemistry 2020, 2020 (15-16) , 1506-1518. https://doi.org/10.1002/ejic.201901304
    80. J. P. H. Oudsen, B. Venderbosch, T. J. Korstanje, M. Tromp. Electronic characterization of redox (non)-innocent Fe 2 S 2 reference systems: a multi K-edge X-ray spectroscopic study. RSC Advances 2020, 10 (2) , 729-738. https://doi.org/10.1039/C9RA08903A
    81. Anke Schoch, Lukas Burkhardt, Roland Schoch, Kai Stührenberg, Matthias Bauer. Hard X-ray spectroscopy: an exhaustive toolbox for mechanistic studies (?). Faraday Discussions 2019, 220 , 113-132. https://doi.org/10.1039/C9FD00070D
    82. Yusuke Sunada, Hideo Nagashima. Hydrosilylation Catalyzed by Base Metals. 2019, 417-437. https://doi.org/10.1002/9783527814787.ch11
    83. Ban Wang, Isaac G. Howard, Jackson W. Pope, Eric D. Conte, Yongming Deng. Bis(imino)pyridine iron complexes for catalytic carbene transfer reactions. Chemical Science 2019, 10 (34) , 7958-7963. https://doi.org/10.1039/C9SC02189B
    84. Jitendrasingh Rajpurohit, Maheswaran Shanmugam. The molecular and electronic structure of an unusual cobalt NNO pincer ligand complex. Dalton Transactions 2019, 48 (21) , 7378-7387. https://doi.org/10.1039/C9DT00056A
    85. Leslie D. Field, Hsiu L. Li, Scott J. Dalgarno, Ruaraidh D. McIntosh. Ammonia and Hydrazine from Coordinated Dinitrogen by Complexes of Iron(0). European Journal of Inorganic Chemistry 2019, 2019 (14) , 2006-2011. https://doi.org/10.1002/ejic.201900058
    86. Adam D. Piascik, Andrew E. Ashley. Group 8 Transition Metal–Dinitrogen Complexes. 2019, 285-335. https://doi.org/10.1002/9783527344260.ch6
    87. Cai-Hong Guo, Dandan Yang, Xiaoyan Liu, Xiang Zhang, Haijun Jiao. Exploring the mechanism of alkene hydrogenation catalyzed by defined iron complex from DFT computation. Journal of Molecular Modeling 2019, 25 (3) https://doi.org/10.1007/s00894-019-3942-6
    88. Andrei Chirila, Braja Gopal Das, Petrus F. Kuijpers, Vivek Sinha, Bas de Bruin. Application of Stimuli‐Responsive and “Non‐innocent” Ligands in Base Metal Catalysis. 2019, 1-31. https://doi.org/10.1002/9783527699087.ch1
    89. Christina Römelt, Thomas Weyhermüller, Karl Wieghardt. Structural characteristics of redox-active pyridine-1,6-diimine complexes: Electronic structures and ligand oxidation levels. Coordination Chemistry Reviews 2019, 380 , 287-317. https://doi.org/10.1016/j.ccr.2018.09.018
    90. Maximilian Fritz, Sven Schneider. The Renaissance of Base Metal Catalysis Enabled by Functional Ligands. 2019, 1-36. https://doi.org/10.1007/430_2019_48
    91. Ryan J. Martinie, Elizabeth J. Blaesi, J. Martin Bollinger, Carsten Krebs, Kenneth D. Finkelstein, Christopher J. Pollock. Two‐Color Valence‐to‐Core X‐ray Emission Spectroscopy Tracks Cofactor Protonation State in a Class I Ribonucleotide Reductase. Angewandte Chemie 2018, 130 (39) , 12936-12940. https://doi.org/10.1002/ange.201807366
    92. Ryan J. Martinie, Elizabeth J. Blaesi, J. Martin Bollinger, Carsten Krebs, Kenneth D. Finkelstein, Christopher J. Pollock. Two‐Color Valence‐to‐Core X‐ray Emission Spectroscopy Tracks Cofactor Protonation State in a Class I Ribonucleotide Reductase. Angewandte Chemie International Edition 2018, 57 (39) , 12754-12758. https://doi.org/10.1002/anie.201807366
    93. Tabea Buban, Sarah Puhl, Peter Burger, Marc H. Prosenc, Jürgen Heck. Magnetic Properties of One-Dimensional Stacked Metal Complexes. 2018, 89-116. https://doi.org/10.1007/978-3-319-99558-8_5
    94. Juan Cámpora, Antonio Rodríguez-Delgado, Pilar Palma. σ-Organometallic Chemistry With 2,6-Bis(imino)pyridine Ligands. 2018, 539-586. https://doi.org/10.1016/B978-0-12-812931-9.00026-8
    95. Zekai Lin, Nathan C. Thacker, Takahiro Sawano, Tasha Drake, Pengfei Ji, Guangxu Lan, Lingyun Cao, Shubin Liu, Cheng Wang, Wenbin Lin. Metal–organic layers stabilize earth-abundant metal–terpyridine diradical complexes for catalytic C–H activation. Chemical Science 2018, 9 (1) , 143-151. https://doi.org/10.1039/C7SC03537C
    96. Anna Hanft, Crispin Lichtenberg. Aminotroponiminates: ligand-centred, reversible redox events under oxidative conditions in sodium and bismuth complexes. Dalton Transactions 2018, 47 (31) , 10578-10589. https://doi.org/10.1039/C8DT01019F
    97. Johanna Flock, Beate Steller, Petra Unger, Birgit Gerke, Rainer Pöttgen, Roland C. Fischer. Iminopyridine ligand complexes of group 14 dihalides and ditriflates – neutral chelates and ion pair formation. Zeitschrift für Naturforschung B 2017, 72 (11) , 883-894. https://doi.org/10.1515/znb-2017-0128
    98. Weiyi Li, Yajing Lyu, Huifang Zhang, Maoqin Zhu, Hanping Tang. A theoretical study on the unusual square-planar structure of bis(imino)pyridine-ligated Group 13 complexes. Dalton Transactions 2017, 46 (1) , 106-115. https://doi.org/10.1039/C6DT03775E
    99. Shogo Kuriyama, Kazuya Arashiba, Kazunari Nakajima, Yuki Matsuo, Hiromasa Tanaka, Kazuyuki Ishii, Kazunari Yoshizawa, Yoshiaki Nishibayashi. Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand. Nature Communications 2016, 7 (1) https://doi.org/10.1038/ncomms12181
    100. Joanna K. Kowalska, Frederico A. Lima, Christopher J. Pollock, Julian A. Rees, Serena DeBeer. A Practical Guide to High‐resolution X‐ray Spectroscopic Measurements and their Applications in Bioinorganic Chemistry. Israel Journal of Chemistry 2016, 56 (9-10) , 803-815. https://doi.org/10.1002/ijch.201600037
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    Cite this: Inorg. Chem. 2012, 51, 6, 3770–3785
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