Structures, Thermal Properties, and Reactivities of Cationic Rh–cod Complexes in Solid State (cod = 1,5-Cyclooctadiene)

This work was financially supported by KAKENHI (grant

number: 20H02756) from the Japan Society for the Promotion

of Science (JSPS) and a Grant-in-Aid for JSPS Research

Fellows (grant number: 21J12056). We are grateful to the

anonymous reviewers for their valuable comments.

(1) Ojima, I.; Vu, A. T.; Bonafoux, D. Product Class 5:

Organometallic Complexes of Rhodium. In Science of Synthesis;

Lautens, M., Ed.; Thieme Verlag, 2001; pp 531−616.

(2) Garralda, M. A.; Oro, L. A. Cationic Rhodium(I) Diolefin

Complexes. Transition Met. Chem. 1980, 5, 65−73.

(3) Osborn, J. A.; Schrock, R. R. Coordinatively Unsaturated

Cationic Complexes of Rhodium(I), Iridium(I), Palladium(II), and

Platinum(II). Generation, Synthetic Utility, and Some Catalytic

Studies. J. Am. Chem. Soc. 1971, 93, 3089−3091.

(4) Emerson-King, J.; Knighton, R. C.; Gyton, M. R.; Chaplin, A. B.

Rotaxane Synthesis Exploiting the M(I)/M(III) Redox Couple.

Dalton Trans. 2017, 46, 11645−11655.

(5) Wender, P. A.; Williams, T. J. [(arene)Rh(cod)]+ Complexes as

Catalysts for [5+2] Cycloaddition Reactions. Angew. Chem., Int. Ed.

2002, 41, 4550−4553.

(6) Kang, S. O.; Lynch, V. M.; Day, V. W.; Anslyn, E. V. Enthalpy- vs

Entropy-Driven Complexation of Homoallylic Alcohols by Rhodium(I) Complexes. Organometallics 2011, 30, 6233−6240.

(7) Toda, F., Ed.; Organic Solid State Reactions; Springer: Berlin

Heidelberg, 2005.

(8) Sheng, M.; Yang, Q.; Huff, D.; Schafer, A. G.; Tucker, C.; Valco,

D. Thermal Instability and Associated Potential Safety Hazards of

Rhodium(I) Precatalyst Complexes with Weakly Coordinated

Ligands. Org. Process Res. Dev. 2021, 25, 1054−1064.

(9) Togni, A.; Hayashi, T., Eds.; Ferrocenes: Homogeneous Catalysis,

Organic Synthesis, Materials Science; Wiley-VCH Verlag: Weinheim,

Germany, 1995.

(10) Stepnicka, P., Ed.; Ferrocenes: Ligands, Materials and

Biomolecules; Wiley-Blackwell: Hoboken, NJ, 2008.

(11) Webb, R. J.; Lowery, M. D.; Shiomi, Y.; Sorai, M.; Wittebort, R.

J.; Hendrickson, D. N. Ferrocenium Hexafluorophosphate: Molecular

Dynamics in the Solid State. Inorg. Chem. 1992, 31, 5211−5219.

(12) Grepioni, F.; Cojazzi, G.; Draper, S. M.; Scully, N.; Braga, D.

Crystal Forms of Hexafluorophosphate Organometallic Salts and the

Importance of Charge-Assisted C−H—F Hydrogen Bonds. Organometallics 1998, 17, 296−307.

(13) Mochida, T.; Funasako, Y.; Ishida, M.; Saruta, S.; Kosone, T.;

Kitazawa, T. Crystal Structures and Phase Sequences of Metallocenium Salts with Fluorinated Anions: Effects of Molecular Size and

Symmetry on Phase Transitions to Ionic Plastic Crystals. Chem. −Eur.

J. 2016, 22, 15725−15732.

(14) Tominaga, T.; Ueda, T.; Mochida, T. Effect of Substituents and

Anions on the Phase Behavior of Ru(II) Sandwich Complexes:

ASSOCIATED CONTENT

sı Supporting Information

The Supporting Information is available free of charge at

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Article

AUTHOR INFORMATION

Corresponding Author

Tomoyuki Mochida − Department of Chemistry, Graduate

School of Science and Research Center for Membrane and

Film Technology, Kobe University, Kobe, Hyogo 657-8501,

2178

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Exploring the Boundaries between Ionic Liquids and Ionic Plastic

Crystals. Phys. Chem. Chem. Phys. 2017, 19, 4352−4359.

(15) Mochida, T.; Ishida, M.; Tominaga, T.; Takahashi, K.; Sakurai,

T.; Ohta, H. Paramagnetic Ionic Plastic Crystals Containing the

Octamethylferrocenium Cation: Counteranion Dependence of Phase

Transitions and Crystal Structures. Phys. Chem. Chem. Phys. 2018, 20,

3019−3028.

(16) Kimata, H.; Mochida, T. Effects of Molecular Structure on

Phase Transitions of Ionic Plastic Crystals Containing Cationic

Sandwich Complexes. Cryst. Growth Des. 2018, 18, 7562−7569.

(17) Pringle, J. M. Recent Progress in the Development and Use of

Organic Ionic Plastic Crystal Electrolytes. Phys. Chem. Chem. Phys.

2013, 15, 1339−1351.

(18) Ishida, H.; Iwachido, T.; Hayama, N.; Ikeda, R.; Terashima, M.;

Nakamura, D. Self-Diffusion and Reorientation of Methylammonium

Ions in (CH3NH3)2ZnCl4 Crystals as Studied by 1H-NMR. Z.

Naturforsch., A 1989, 44, 741−746.

(19) Matsumoto, K.; Harinaga, U.; Tanaka, R.; Koyama, A.;

Hagiwara, R.; Tsunashima, K. The Structural Classification of the

Highly Disordered Crystal Phases of [Nn][BF4], [Nn][PF6], [Pn][BF4], and [Pn][PF6] Salts (Nn+ = Tetraalkylammonium and Pn+ =

Tetraalkylphosphonium). Phys. Chem. Chem. Phys. 2014, 16, 23616−

23626.

(20) Enomoto, T.; Kanematsu, S.; Tsunashima, K.; Matsumoto, K.;

Hagiwara, R. Physicochemical Properties and Plastic Crystal

Structures of Phosphonium Fluorohydrogenate Salts. Phys. Chem.

Chem. Phys. 2011, 13, 12536−12544.

(21) Zhou, Z.-B.; Matsumoto, H. Lithium-Doped, Organic Ionic

Plastic Crystal Electrolytes Exhibiting High Ambient-Temperature

Conductivities. Electrochem. Commun. 2007, 9, 1017−1022.

(22) Hayasaki, T.; Hirakawa, S.; Honda, H. New Ionic Plastic

Crystals of NR4BEt3Me (R = Me and Et) and NRxR′4−xBEt3Me (R =

Et, R′ = Me and Pr, x = 1−3) in a New Class of Plastic Crystals. Bull.

Chem. Soc. Jpn. 2013, 86, 993−1001.

(23) Yunis, R.; Newbegin, T. W.; Hollenkamp, A. F.; Pringle, J. M.

Ionic Liquids and Plastic Crystals with a Symmetrical Pyrrolidinium

Cation. Mater. Chem. Front. 2018, 2, 1207−1214.

(24) MacFarlane, D. R.; Huang, J.; Forsyth, M. Lithium-Doped

Plastic Crystal Electrolytes Exhibiting Fast Ion Conduction for

Secondary Batteries. Nature 1999, 402, 792−794.

(25) Henderson, W. A.; Herstedt, M.; Young, V. G.; Passerini, S.; De

Long, H. C.; Trulove, P. C. New Disordering Mode for TFSI−

Anions: The Nonequilibrium, Plastic Crystalline Structure of

Et4NTFSI. Inorg. Chem. 2006, 45, 1412−1414.

(26) Harada, J. Plastic/Ferroelectric Molecular Crystals: Ferroelectric Performance in Bulk Polycrystalline Forms. APL Mater. 2021,

9, No. 020901.

(27) Basile, A.; Hilder, M.; Makhlooghiazad, F.; Pozo-Gonzalo, C.;

MacFarlane, D. R.; Howlett, P. C.; Forsyth, M. Ionic Liquids and

Organic Ionic Plastic Crystals: Advanced Electrolytes for Safer High

Performance Sodium Energy Storage Technologies. Adv. Energy

Mater. 2018, 8, No. 1703491.

(28) Zhu, H.; MacFarlane, D. R.; Pringle, J. M.; Forsyth, M. Organic

Ionic Plastic Crystals as Solid-State Electrolytes. Trends Chem. 2019,

1, 126−140.

(29) Yoshizawa-Fujita, M.; Nakazawa, M.; Takeoka, Y.; Rikukawa,

M. Phase Transitions and Ionic Conductivity of Ionic Plastic Crystals

Based on Pyrrolidinium Cations and Dihydrogen Phosphate Anion. J.

Non-Cryst. Solids: X 2022, 13, No. 100078.

(30) Su, Y.; Liu, G.; Xie, B.; Fu, D.; Wang, D. Crystallization

Features of Normal Alkanes in Confined Geometry. Acc. Chem. Res.

2014, 47, 192−201.

(31) Shimizu, T.; Tanaka, S.; Onoda-Yamamuro, N.; Ishimaru, S.;

Ikeda, R. New Rotator Phase Revealed in Di-n-Alkylammonium

Bromides Studied by Solid-State NMR, Powder XRD, Electrical

Conductivity and Thermal Measurements. J. Chem. Soc., Faraday

Trans. 1997, 93, 321−326.

Article

(32) Pringle, J. M.; Shekibi, Y.; MacFarlane, D. R.; Forsyth, M. The

Influence of Different Nanoparticles on a Range of Organic Ionic

Plastic Crystals. Electrochim. Acta 2010, 55, 8847−8854.

(33) Yamada, Y.; Kashimoto, E.; Honda, H. New Chemical Family

of [n-CxH(2x+1)NEt3][BEt3Me] Showing Ionic Plastic-Crystal (x = 4,

5), Rotator-Crystal (x = 6, 7) and Liquid-Crystal Phases (x = 8−16).

Bull. Chem. Soc. Jpn. 2019, 92, 1289−1298.

(34) Green, M.; Kuc, T. A. Cationic Transition-Metal Complexes.

Part II. The Reaction of Arenes and Olefins with Bis(cyclo-octa-1,5diene or Norbornadiene)Rhodium Tetrafluoroborate. J. Chem. Soc.,

Dalton Trans. 1972, 832−839.

(35) RajanBabu, T. V.; Ayers, T. A.; Halliday, G. A.; You, K. K.;

Calabrese, J. C. Carbohydrate Phosphinites as Practical Ligands in

Asymmetric Catalysis: Electronic Effects and Dependence of

Backbone Chirality in Rh-Catalyzed Asymmetric Hydrogenations

Synthesis of R- or S-Amino Acids Using Natural Sugars as Ligand

Precursors. J. Org. Chem. 1997, 62, 6012−6028.

(36) Song, G.; Zhang, Y.; Su, Y.; Deng, W.; Han, K.; Li, X. PyridineBased N-Heterocyclic Carbene Hydride Complexes of Iridium via C−

H Activation. Organometallics 2008, 27, 6193−6201.

(37) Kar, M.; Matuszek, K.; MacFarlane, D. R. Ionic Liquids. In

Kirk-Othmer Encyclopedia of Chemical Technology; John Wiley & Sons,

Inc.: Hoboken, 2019.

(38) Sas, O. G.; Domínguez, I.; González, B.; Domínguez, Á . LiquidLiquid Extraction of Phenolic Compounds from Water Using Ionic

Liquids: Literature Review and New Experimental Data Using

[C2mim]FSI. J. Environ. Manage. 2018, 228, 475−482.

(39) Weller, A. S.; Mahon, M. F.; Steed, J. W. Rhodium

Cyclooctadiene Complexes of the Weakly Co-Ordinating Carborane

Anion [Closo-CB11H12]−. Isolation and Crystal Structures of

[(COD)Rh(η2-CB11H12)] and [(COD)Rh(THF)2][CB11H12]. J.

Organomet. Chem. 2000, 614−615, 113−119.

(40) Tang, Y.; Yu, B. Coinage Metal (Bisfluorosulfonyl)Imide

Complexes: Preparation, Characterization, and Catalytic Applications.

Eur. J. Inorg. Chem. 2020, 2020, 107−118.

(41) Polyakov, O. G.; Ivanova, S. M.; Gaudinski, C. M.; Miller, S.

M.; Anderson, O. P.; Strauss, S. H. Cu(CO)2(N(SO2CF3)2). The

First Structurally Characterized Copper(I) Polycarbonyl. Organometallics 1999, 18, 3769−3771.

(42) Begley, M. J.; Sowerby, D. B.; Verma, R. D.; Vig, A. Structure of

the Silver Imidodi(sulphuryl fluoride)-Benzene Solvate AgN(SO2F)2·

C6H6. J. Organomet. Chem. 1994, 481, 243−246.

(43) Xiao, J.; Cui, Y.; Li, C.; Xu, H.; Zhai, Y.; Zhang, X.; Ma, S.

Room Temperature Allenation of Terminal Alkynes with Aldehydes.

Angew. Chem., Int. Ed. 2021, 60, 25708−25713.

(44) Bowring, M. A.; Bergman, R. G.; Tilley, T. D. Pt-Catalyzed C−

C Activation Induced by C−H Activation. J. Am. Chem. Soc. 2013,

135, 13121−13128.

(45) Sievert, A. C.; Muetterties, E. L. Arene Transition-Metal

Chemistry. 5. Arene Ligand Exchange and Reactivity in η6-Arene

Iridium(I) Complexes. Inorg. Chem. 1981, 20, 489−501.

(46) Guzel, B.; Omary, M. A.; Fackler, J. P.; Akgerman, A. Synthesis

and Characterization of {[(COD)Rh(bis-(2R,3R)-2,5-diethylphospholanobenzene)]+BARF−} for Use in Homogeneous Catalysis in

Supercritical Carbon Dioxide. Inorg. Chim. Acta 2001, 325, 45−50.

(47) Green, M.; Kuc, T. A.; Taylor, S. H. Cationic Transition-Metal

Complexes. Part I. Synthesis and Reactions of Bis(diene)-Rhodium

and -Iridium Tetrafluoroborates. J. Chem. Soc. A 1971, 2334−2337.

(48) Mingos, D. M. P.; Rohl, A. L. Size and Shape Characteristics of

Inorganic Molecules and Ions and Their Relevance to Molecular

Packing Problems. J. Chem. Soc., Dalton Trans. 1991, 3419−3425.

(49) Atkins, P.; Overton, T. Shriver and Atkins’ Inorganic Chemistry;

Oxford University Press: New York, 2010.

(50) Dahlenburg, L.; Osthoff, N.; Heinemann, F. W. Bis(η4-Cycloocta-1,5-Diene)Rhodium(I) Trifluoromethanesulfonate. Acta Crystallogr., Sect. E: Struct. Rep. Online 2001, 57, 117−118.

(51) Baenziger, N. C.; Mottel, E. A.; Doyle, J. R. Structure of

Bis(1,5-cyclooctadiene)rhodium(I) Hexacarbonyl-tri-μ-chloro2179

https://doi.org/10.1021/acs.inorgchem.2c03865

Inorg. Chem. 2023, 62, 2169−2180

Inorganic Chemistry

pubs.acs.org/IC

dirhenate(I). Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1991,

47, 539−541.

(52) Kotani, Y.; Honda, H. 1H and 13C NMR Studies on New Ionic

Plastic Crystals Constructed by Ellipsoidal Cations with [BEt3Me]

Anion. Bull. Chem. Soc. Jpn. 2019, 92, 768−778.

(53) Rice, D. M.; Wittebort, R. J.; Griffin, R. G.; Meirovitch, E.;

Stimson, E. R.; Meinwald, Y. C.; Freed, J. H.; Scheraga, H. A.

Rotational Jumps of the Tyrosine Side Chain in Crystalline

Enkephalin. 2H NMR Line Shapes for Aromatic Ring Motions in

Solids. J. Am. Chem. Soc. 1981, 103, 7707−7710.

(54) Emsley, J. W.; Lindon, J. C.; Tabony, J. Measurement of

Deuterium Quadrupole Coupling Constants of CD3 Groups by 1H−

{2H} N.M.R. Studies of Nematic Solutions. Mol. Phys. 1973, 26,

1499−1509.

(55) Kimata, H.; Sumitani, R.; Mochida, T. Phase Transitions and

Crystal Structures of Ionic Plastic Crystals Comprising Quaternary

Ammonium Cations and Carborane Anion. Chem. Lett. 2019, 48,

859−862.

(56) Sumitani, R.; Funasako, Y.; Mochida, T. Thermal Properties

and Crystal Structures of Ruthenium-Containing Photoreactive Ionic

Liquids with Short Substituents. J. Mol. Liq. 2020, 318, No. 114071.

(57) Matsumoto, K.; Oka, T.; Nohira, T.; Hagiwara, R. Polymorphism of Alkali Bis(fluorosulfonyl)amides (M[N(SO2F)2], M =

Na, K, and Cs). Inorg. Chem. 2013, 52, 568−576.

(58) Mochida, T.; Funasako, Y.; Inagaki, T.; Li, M.-J.; Asahara, K.;

Kuwahara, D. Crystal Structures and Phase-Transition Dynamics of

Cobaltocenium Salts with Bis(perfluoroalkylsulfonyl)amide Anions:

Remarkable Odd-Even Effect of the Fluorocarbon Chains in the

Anion. Chem. −Eur. J. 2013, 19, 6257−6264.

(59) Sumitani, R.; Mochida, T. Thermal Properties, Crystal

Structures, and Photoreactivity of Ru-Containing Ionic Liquids with

Sulfur-Containing Substituents. J. Mol. Liq. 2021, 344, No. 117784.

(60) de Bruin, B.; Brands, J. A.; Donners, J. J. J. M.; Donners, M. P.

J.; de Gelder, R.; Smits, J. M. M.; Gal, A. W.; Spek, A. L. Selective

Oxidation of [RhI(cod)]+ by H2O2 and O2. Chem. −Eur. J. 1999, 5,

2921−2936.

(61) de Bruin, B.; Boerakker, M. J.; Donners, J. J. J. M.; Christiaans,

B. E. C.; Schlebos, P. P. J.; de Gelder, R.; Smits, J. M. M.; Spek, A. L.;

Gal, A. W. Oxidation of RhI(olefin) Fragments to 2-Rhoda(III)Oxetanes. Angew. Chem., Int. Ed. 1997, 36, 2064−2067.

(62) Fernandez-Bartolome, E.; Martinez-Martinez, A.; ResinesUrien, E.; Piñeiro-Lopez, L.; Costa, J. S. Reversible Single-Crystalto-Single-Crystal Transformations in Coordination Compounds

Induced by External Stimuli. Coord. Chem. Rev. 2022, 452,

No. 214281.

(63) Braga, D.; Maini, L.; Grepioni, F. Mechanochemical

Preparation of Co-Crystals. Chem. Soc. Rev. 2013, 42, 7638−7648.

(64) Green, M.; Kuc, T. A.; Taylor, S. H. The Synthesis and Some

Reactions of Bis(acetonitrile)(diene)-Rhodium and -Iridium Tetrafluoroborate. J. Chem. Soc., Dalton Trans. 1970, 1553−1554.

(65) Tiripicchio, A.; Camellini, M. T.; Claver, C.; Ruiz, A.; Oro, L.

A. Diolefin Cationic Rhodium Complexes with Sulfur Donors. X-Ray

Structure of [Rh(NBD)2(SEt2)]ClO4. J. Organomet. Chem. 1983, 241,

77−86.

(66) Dorta, R.; Rozenberg, H.; Shimon, L. J. W.; Milstein, D.

Dimethylsulfoxide as a Ligand for RhI and IrI Complexes�Isolation,

Structure, and Reactivity towards X-H Bonds (X = H, OH, OCH3).

Chem.−Eur. J. 2003, 9, 5237−5249.

(67) Bats, J. W.; Rivas Nass, A.; Hashmi, A. S. K. Low-Temperature

Phase of Diaqua(1,5-cyclooctadiene)rhodium(I) Trifluoromethanesulfonate. Acta Crystallogr., Sect. E: Struct. Rep. Online 2004, 60, 85−

87.

(68) Schenck, T. G.; Downes, J. M.; Milne, C. R. C.; Mackenzie, P.

B.; Boucher, T. G.; Whelan, J.; Bosnich, B. Bimetallic Reactivity.

Synthesis of Bimetallic Complexes Containing a Bis(phosphino)pyrazole Ligand. Inorg. Chem. 1985, 24, 2334−2337.

(69) Shelly, K.; Finster, D. C.; Lee, Y. J.; Scheidt, W. R.; Reed, C. A.

η1-Benzene Coordination: The Synthesis and X-Ray Crystal Structure

Article

of a Novel Silver Salt of the Weakly Coordinating Carborane Anion

B11CH12−. J. Am. Chem. Soc. 1985, 107, 5955−5959.

(70) Davis, J. H.; Jeffrey, K. R.; Bloom, M.; Valic, M. I.; Higgs, T. P.

Quadrupolar Echo Deuteron Magnetic Resonance Spectroscopy in

Ordered Hydrocarbon Chains. Chem. Phys. Lett. 1976, 42, 390−394.

(71) Sheldrick, G. M. A Short History of SHELX. Acta Crystallogr.,

Sect. A: Found. Crystallogr. 2008, 64, 112−122.

(72) APEX3, v2015.52; Bruker AXS Inc.: Madison, WI, 2015.

(73) Macrae, C. F.; Bruno, I. J.; Chisholm, J. A.; Edgington, P. R.;

McCabe, P.; Pidcock, E.; Rodriguez-Monge, L.; Taylor, R.; van de

Streek, J.; Wood, P. A. Mercury CSD 2.0 − New Features for the

Visualization and Investigation of Crystal Structures. J. Appl.

Crystallogr. 2008, 41, 466−470.

(74) Spek, A. L. Structure Validation in Chemical Crystallography.

Acta Crystallogr., Sect. D: Biol. Crystallogr. 2009, 65, 148−155.

(75) Sheldrick, G. M. TWINABS v2012/1; University of Göttingen,

2012.

(76) XPREP v2014/2; Bruker AXS Inc.: Madison, WI, 2014.

2180

https://doi.org/10.1021/acs.inorgchem.2c03865

Inorg. Chem. 2023, 62, 2169−2180

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