Isolation of (CO)1– and (CO2)1– Radical Complexes of Rare Earths via Ln(NR2)3/K Reduction and [K2(18-crown-6)2]2+ OligomerizationClick to copy article linkArticle link copied!
Abstract
Deep-blue solutions of Y2+ formed from Y(NR2)3 (R = SiMe3) and excess potassium in the presence of 18-crown-6 at −45 °C under vacuum in diethyl ether react with CO at −78 °C to form colorless crystals of the (CO)1– radical complex, {[(R2N)3Y(μ-CO)2][K2(18-crown-6)2]}n, 1. The polymeric structure contains trigonal bipyramidal [(R2N)3Y(μ-CO)2]2– units with axial (CO)1– ligands linked by [K2(18-crown-6)2]2+ dications. Byproducts such as the ynediolate, [(R2N)3Y]2(μ-OC≡CO){[K(18-crown-6)]2(18-crown-6)}, 2, in which two (CO)1– anions are coupled to form (OC≡CO)2–, and the insertion/rearrangement product, {(R2N)2Y[OC(═CH2)Si(Me2)NSiMe3]}[K(18-crown-6)], 3, are common in these reactions that give variable results depending on the specific reaction conditions. The CO reduction in the presence of THF forms a solvated variant of 2, the ynediolate [(R2N)3Y]2(μ-OC≡CO)[K(18-crown-6)(THF)2]2, 2a. CO2 reacts analogously with Y2+ to form the (CO2)1– radical complex, {[(R2N)3Y(μ-CO2)2][K2(18-crown-6)2]}n, 4, that has a structure similar to that of 1. Analogous (CO)1– and (OC≡CO)2– complexes of lutetium were isolated using Lu(NR2)3/K/18-crown-6: {[(R2N)3Lu(μ-CO)2][K2(18-crown-6)2]}n, 5, [(R2N)3Lu]2(μ-OC≡CO){[K(18-crown-6)]2(18-crown-6)}, 6, and [(R2N)3Lu]2(μ-OC≡CO)[K(18-crown-6)(Et2O)2]2, 6a.
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(36)
, 24770-24775. https://doi.org/10.1021/jacs.4c09021
- Vanessa R. Landaeta, Thomas M. Horsley Downie, Robert Wolf. Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis. Chemical Reviews 2024, 124
(4)
, 1323-1463. https://doi.org/10.1021/acs.chemrev.3c00121
- Haihan Yan, Botao Wu, Junnian Wei, Wen-Xiong Zhang. Insight into the Ligand-to-Ligand Charge-Transfer Process in Rare-Earth-Metal Diradical Complexes. Inorganic Chemistry 2023, 62
(21)
, 8052-8057. https://doi.org/10.1021/acs.inorgchem.3c00900
- Amanda B. Chung, Cary R. Stennett, William N. G. Moore, Ming Fang, Joseph W. Ziller, William J. Evans. Reductive C–O Cleavage of Ethereal Solvents and 18-Crown-6 in Ln(NR2)3/KC8 Reactions (R = SiMe3). Inorganic Chemistry 2023, 62
(14)
, 5854-5862. https://doi.org/10.1021/acs.inorgchem.3c00689
- Johanna M. Uher, Matthias R. Steiner, Johann A. Hlina. Mono- and Disamarium Azacryptand Complexes: A Platform for Cooperative Rare-Earth Metal Chemistry. Inorganic Chemistry 2022, 61
(14)
, 5539-5546. https://doi.org/10.1021/acs.inorgchem.1c03989
- Han-Ying Liu, Ryan J. Schwamm, Samuel E. Neale, Michael S. Hill, Claire L. McMullin, Mary F. Mahon. Reductive Dimerization of CO by a Na/Mg(I) Diamide. Journal of the American Chemical Society 2021, 143
(42)
, 17851-17856. https://doi.org/10.1021/jacs.1c09467
- Amanda B. Chung, Austin J. Ryan, Ming Fang, Joseph W. Ziller, William J. Evans. Reductive Reactivity of the 4f75d1 Gd(II) Ion in {GdII[N(SiMe3)2]3}−: Structural Characterization of Products of Coupling, Bond Cleavage, Insertion, and Radical Reactions. Inorganic Chemistry 2021, 60
(20)
, 15635-15645. https://doi.org/10.1021/acs.inorgchem.1c02241
- Wenqing Wang, Yaping Wen, Jian Su, Haibo Ma, Hai-Ying Wang, Mohamedally Kurmoo, Jing-Lin Zuo. Carbon Dioxide (CO2) Fixation: Linearly Bridged Zn2 Paddlewheel Nodes by CO2 in a Metal–Organic Framework. Inorganic Chemistry 2019, 58
(23)
, 16040-16046. https://doi.org/10.1021/acs.inorgchem.9b02548
- David H. Woen, Guo P. Chen, Joseph W. Ziller, Timothy J. Boyle, Filipp Furche, and William J. Evans . End-On Bridging Dinitrogen Complex of Scandium. Journal of the American Chemical Society 2017, 139
(42)
, 14861-14864. https://doi.org/10.1021/jacs.7b08456
- Jordan F. Corbey, David H. Woen, Chad T. Palumbo, Megan E. Fieser, Joseph W. Ziller, Filipp Furche, and William J. Evans . Ligand Effects in the Synthesis of Ln2+ Complexes by Reduction of Tris(cyclopentadienyl) Precursors Including C–H Bond Activation of an Indenyl Anion. Organometallics 2015, 34
(15)
, 3909-3921. https://doi.org/10.1021/acs.organomet.5b00500
- Rainer Zitz, Johann Hlina, Karl Gatterer, Christoph Marschner, Tibor Szilvási, and Judith Baumgartner . Neutral “Cp-Free” Silyl-Lanthanide(II) Complexes: Synthesis, Structure, and Bonding Analysis. Inorganic Chemistry 2015, 54
(14)
, 7065-7072. https://doi.org/10.1021/acs.inorgchem.5b01072
- Alexandre Hervé, Yamina Bouzidi, Jean-Claude Berthet, Lotfi Belkhiri, Pierre Thuéry, Abdou Boucekkine, and Michel Ephritikhine . U–CN versus Ce–NC Coordination in Trivalent Complexes Derived from M[N(SiMe3)2]3 (M = Ce, U). Inorganic Chemistry 2014, 53
(13)
, 6995-7013. https://doi.org/10.1021/ic500939t
- Matthew R. MacDonald, Jefferson E. Bates, Joseph W. Ziller, Filipp Furche, and William J. Evans . Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr2+, Gd2+, Tb2+, and Lu2+. Journal of the American Chemical Society 2013, 135
(26)
, 9857-9868. https://doi.org/10.1021/ja403753j
- Shuangliu Zhou, Zhangshuan Wu, Lingmin Zhou, Shaowu Wang, Lijun Zhang, Xiancui Zhu, Yun Wei, Jinhua Zhai, and Jie Wu . Controlled Synthesis of Racemic Indenyl Rare-Earth Metal Complexes via the Cooperation between the Intramolecular Coordination of Donor Atoms and a Bridge. Inorganic Chemistry 2013, 52
(11)
, 6417-6426. https://doi.org/10.1021/ic4003109
- Megan E. Fieser, Jefferson E. Bates, Joseph W. Ziller, Filipp Furche, and William J. Evans . Dinitrogen Reduction via Photochemical Activation of Heteroleptic Tris(cyclopentadienyl) Rare-Earth Complexes. Journal of the American Chemical Society 2013, 135
(10)
, 3804-3807. https://doi.org/10.1021/ja400664s
- David P. Mills, Lyndsay Soutar, Oliver J. Cooper, William Lewis, Alexander J. Blake, and Stephen T. Liddle . Reactivity of the Yttrium Alkyl Carbene Complex [Y(BIPM)(CH2C6H5)(THF)] (BIPM = {C(PPh2NSiMe3)2})2–: From Insertions, Substitutions, and Additions to Nontypical Transformations. Organometallics 2013, 32
(5)
, 1251-1264. https://doi.org/10.1021/om3010178
- Joy H. Farnaby, Ming Fang, Joseph W. Ziller, and William J. Evans . Expanding Yttrium Bis(trimethylsilylamide) Chemistry Through the Reaction Chemistry of (N2)2–, (N2)3–, and (NO)2– Complexes. Inorganic Chemistry 2012, 51
(20)
, 11168-11176. https://doi.org/10.1021/ic301778q
- Matthew R. MacDonald, Jefferson E. Bates, Megan E. Fieser, Joseph W. Ziller, Filipp Furche, and William J. Evans . Expanding Rare-Earth Oxidation State Chemistry to Molecular Complexes of Holmium(II) and Erbium(II). Journal of the American Chemical Society 2012, 134
(20)
, 8420-8423. https://doi.org/10.1021/ja303357w
- Qing You, Jiamin Cai, Jie Zhang, Xigeng Zhou. Tuning the reactivity of an yttrium complex bearing a functionalized silylamido ligand using solvated KCl. Inorganic Chemistry Frontiers 2024, 11
(21)
, 7501-7511. https://doi.org/10.1039/D4QI01882F
- Ahmadreza Rajabi, Robin Grotjahn, Dmitrij Rappoport, Filipp Furche. A DFT perspective on organometallic lanthanide chemistry. Dalton Transactions 2024, 104 https://doi.org/10.1039/D3DT03221C
- Ana M. Geer, Deborah L. Kays, Laurence J. Taylor. Homogeneous Carbon Monoxide Homologation. 2023, 813-846. https://doi.org/10.1002/9783527830237.ch23
- Jiamin Cai, Jie Zhang, Xigeng Zhou. Selective Si–C(sp
3
) bond cleavage of a silyl-bridged amido alkyl ligand in an yttrium complex. Dalton Transactions 2023, 52
(12)
, 3807-3814. https://doi.org/10.1039/D3DT00149K
- Robert J. Ward, Iker del Rosal, Steven P. Kelley, Laurent Maron, Justin R. Walensky. Isolation of C1 through C4 derivatives from CO using heteroleptic uranium(
iii
) metallocene aryloxide complexes. Chemical Science 2023, 14
(8)
, 2024-2032. https://doi.org/10.1039/D2SC06375A
- Na Li, Jinliang Zhang, Jun Matsushima, Cheng Song, Xuwei Luan, Ming Dou, Tao Chen, Lingling Wang. Sensitivity analysis of seismic attributes and oil reservoir predictions based on jointing wells and seismic data – A case study in the Taoerhe Sag, China. Frontiers in Marine Science 2022, 9 https://doi.org/10.3389/fmars.2022.1011770
- Thomas Simler, Karl N. McCabe, Laurent Maron, Grégory Nocton. CO reductive oligomerization by a divalent thulium complex and CO
2
-induced functionalization. Chemical Science 2022, 13
(25)
, 7449-7461. https://doi.org/10.1039/D2SC01798A
- Keith Izod. Alkyl, carbonyl and cyanide complexes of the group 3 metals and lanthanides. 2022, 3-57. https://doi.org/10.1016/B978-0-12-820206-7.00058-5
- Richard A. Layfield. Lanthanides. 2021, 418-470. https://doi.org/10.1016/B978-0-08-102688-5.00057-X
- Mark R. Crimmin, Richard Y. Kong, Nick Phillips. Coordination and Activation of Alkanes, CO and CO2 at Metal Centres. 2021, 311-362. https://doi.org/10.1016/B978-0-08-102688-5.00055-6
- Ross F. Koby, Timothy P. Hanusa. Macrocyclic Complexes of the Alkali Metals. 2021, 49-65. https://doi.org/10.1016/B978-0-12-409547-2.14810-3
- Uwe Bayer, Reiner Anwander. Carbonyl group and carbon dioxide activation by rare-earth-metal complexes. Dalton Transactions 2020, 49
(48)
, 17472-17493. https://doi.org/10.1039/D0DT03578E
- Sree Ganesh Balasubramani, Guo P. Chen, Sonia Coriani, Michael Diedenhofen, Marius S. Frank, Yannick J. Franzke, Filipp Furche, Robin Grotjahn, Michael E. Harding, Christof Hättig, Arnim Hellweg, Benjamin Helmich-Paris, Christof Holzer, Uwe Huniar, Martin Kaupp, Alireza Marefat Khah, Sarah Karbalaei Khani, Thomas Müller, Fabian Mack, Brian D. Nguyen, Shane M. Parker, Eva Perlt, Dmitrij Rappoport, Kevin Reiter, Saswata Roy, Matthias Rückert, Gunnar Schmitz, Marek Sierka, Enrico Tapavicza, David P. Tew, Christoph van Wüllen, Vamsee K. Voora, Florian Weigend, Artur Wodyński, Jason M. Yu. TURBOMOLE: Modular program suite for
ab initio
quantum-chemical and condensed-matter simulations. The Journal of Chemical Physics 2020, 152
(18)
https://doi.org/10.1063/5.0004635
- Austin J. Ryan, Joseph W. Ziller, William J. Evans. The importance of the counter-cation in reductive rare-earth metal chemistry: 18-crown-6 instead of 2,2,2-cryptand allows isolation of [Y
II
(NR
2
)
3
]
1−
and ynediolate and enediolate complexes from CO reactions. Chemical Science 2020, 11
(7)
, 2006-2014. https://doi.org/10.1039/C9SC05794C
- Fabrizio Ortu, David P. Mills. Low-coordinate rare-earth and actinide complexes. 2019, 1-87. https://doi.org/10.1016/bs.hpcre.2019.05.001
- Evan P. Beaumier, Adam J. Pearce, Xin Yi See, Ian A. Tonks. Modern applications of low-valent early transition metals in synthesis and catalysis. Nature Reviews Chemistry 2019, 3
(1)
, 15-34. https://doi.org/10.1038/s41570-018-0059-x
- Daniel N. Huh, Joseph W. Ziller, William J. Evans. Isolation of reactive Ln(
ii
) complexes with C
5
H
4
Me ligands (Cp
Me
) using inverse sandwich countercations: synthesis and structure of [(18-crown-6)K(μ-Cp
Me
)K(18-crown-6)][Cp
Me
3
Ln
II
] (Ln = Tb, Ho). Dalton Transactions 2018, 47
(48)
, 17285-17290. https://doi.org/10.1039/C8DT03890B
- Kyle A. Grice. Carbon dioxide reduction with homogenous early transition metal complexes: Opportunities and challenges for developing CO 2 catalysis. Coordination Chemistry Reviews 2017, 336 , 78-95. https://doi.org/10.1016/j.ccr.2017.01.007
- David H. Woen, Guo P. Chen, Joseph W. Ziller, Timothy J. Boyle, Filipp Furche, William J. Evans. Solution Synthesis, Structure, and CO
2
Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe
3
)
2
]
3
}
−. Angewandte Chemie 2017, 129
(8)
, 2082-2085. https://doi.org/10.1002/ange.201611758
- David H. Woen, Guo P. Chen, Joseph W. Ziller, Timothy J. Boyle, Filipp Furche, William J. Evans. Solution Synthesis, Structure, and CO
2
Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe
3
)
2
]
3
}
−. Angewandte Chemie International Edition 2017, 56
(8)
, 2050-2053. https://doi.org/10.1002/anie.201611758
- Antonio Pastor, Francisco Montilla, Agustín Galindo. Spectroscopic and Structural Characterization of Carbon Dioxide Transition Metal Complexes. 2017, 1-91. https://doi.org/10.1016/bs.adomc.2017.07.001
- Wolfgang Kaim. Electron Transfer Reactivity of Organometallic Compounds Involving Radical-Forming Noninnocent Ligands. Proceedings of the National Academy of Sciences, India Section A: Physical Sciences 2016, 86
(4)
, 445-457. https://doi.org/10.1007/s40010-016-0304-y
- Megan E. Fieser, David H. Woen, Jordan F. Corbey, Thomas J. Mueller, Joseph W. Ziller, William J. Evans. Raman spectroscopy of the N–N bond in rare earth dinitrogen complexes. Dalton Transactions 2016, 45
(37)
, 14634-14644. https://doi.org/10.1039/C5DT04547A
- Luke J. Murphy, Katherine N. Robertson, Richard A. Kemp, Heikki M. Tuononen, Jason A. C. Clyburne. Structurally simple complexes of CO
2. Chemical Communications 2015, 51
(19)
, 3942-3956. https://doi.org/10.1039/C4CC08510H
- Niall J. English, Morad M. El-Hendawy, Damian A. Mooney, J.M.D. MacElroy. Perspectives on atmospheric CO2 fixation in inorganic and biomimetic structures. Coordination Chemistry Reviews 2014, 269 , 85-95. https://doi.org/10.1016/j.ccr.2014.02.015
- Gerd Meyer. Alle Lanthanide und nun sogar Uran in der Oxidationsstufe +2!. Angewandte Chemie 2014, 126
(14)
, 3620-3622. https://doi.org/10.1002/ange.201311325
- Gerd Meyer. All the Lanthanides Do It and Even Uranium Does Oxidation State +2. Angewandte Chemie International Edition 2014, 53
(14)
, 3550-3551. https://doi.org/10.1002/anie.201311325
- Simon A. Cotton. Lanthanide Amides. 2014, 1-11. https://doi.org/10.1002/9781119951438.eibc2026
- Frank T. Edelmann. Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2012. Coordination Chemistry Reviews 2014, 261 , 73-155. https://doi.org/10.1016/j.ccr.2013.11.008
- Song Yang, Xiancui Zhu, Shuangliu Zhou, Shaowu Wang, Zhijun Feng, Yun Wei, Hui Miao, Liping Guo, Fenhua Wang, Guangchao Zhang, Xiaoxia Gu, Xiaolong Mu. Synthesis, structure, and catalytic activity of novel trinuclear rare-earth metal amido complexes incorporating μ–η
5
:η
1
bonding indolyl and μ
3
-oxo groups. Dalton Trans. 2014, 43
(6)
, 2521-2533. https://doi.org/10.1039/C3DT51107C
- Goutam Nandi, Israel Goldberg. Fixation of CO
2
in bi-layered coordination networks of zinc tetra(4-carboxyphenyl)porphyrin with multi-component [Pr
2
Na
3
(NO
3
)(H
2
O)
3
] connectors. Chem. Commun. 2014, 50
(88)
, 13612-13615. https://doi.org/10.1039/C4CC05601A
- Polly L. Arnold, Zöe R. Turner, Anne I. Germeroth, Ian J. Casely, Gary S. Nichol, Ronan Bellabarba, Robert P. Tooze. Carbon monoxide and carbon dioxide insertion chemistry of f-block N-heterocyclic carbene complexes. Dalton Trans. 2013, 42
(5)
, 1333-1337. https://doi.org/10.1039/C2DT31698F
- Simon A. Cotton. Scandium, yttrium, the lanthanides. Annual Reports Section "A" (Inorganic Chemistry) 2013, 109 , 208. https://doi.org/10.1039/c3ic90017g
- Caroline T. Saouma, Connie C. Lu, Michael W. Day, Jonas C. Peters. CO2 reduction by Fe(i): solvent control of C–O cleavage versus C–C coupling. Chemical Science 2013, 4
(10)
, 4042. https://doi.org/10.1039/c3sc51262b
- Stephen T. Liddle. Lanthanides: Organometallic Chemistry. 2012https://doi.org/10.1002/9781119951438.eibc2082
- Mengtao Ma, Andreas Stasch, Cameron Jones. Magnesium(I) Dimers as Reagents for the Reductive Coupling of Isonitriles and Nitriles. Chemistry – A European Journal 2012, 18
(34)
, 10669-10676. https://doi.org/10.1002/chem.201201030
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