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A Simple Route to Difluorocarbene and Perfluoroalkylidene Complexes of Iridium

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Department of Chemistry, 6128 Burke Laboratory, Dartmouth College, Hanover, New Hampshire 03755, and Department of Chemistry, University of California, San Diego, California 92093-0358
Cite this: J. Am. Chem. Soc. 2005, 127, 43, 15020–15021
Publication Date (Web):October 7, 2005
https://doi.org/10.1021/ja055166k
Copyright © 2005 American Chemical Society

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    Abstract

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    Primary perfluoroalkyl compounds of iridium undergo facile two-electron reduction to afford a simple route to difluorocarbene and perfluoroalkylidene complexes, two of which have been crystallographically characterized. Low-temperature protonation reactions illustrate that the thermodynamic site of protonation depends on the nature of the fluorinated carbene; the difluorocarbene complex undergoes protonation at iridium, while its perfluoroethylidene congener undergoes protonation at carbon.

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     Dartmouth College.

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     University of California at San Diego.

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     Permanent address:  Department of Chemistry, University of Massachusetts Dartmouth, N. Dartmouth, MA 02747.

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    Experimental details for all compounds and CIF files for 3a, 4a, 4b, and 8. This material is available free of charge via the Internet at http://pubs.acs.org.

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    7. Daniel J. Harrison, Serge I. Gorelsky, Graham M. Lee, Ilia Korobkov, and R. Tom Baker . Cobalt Fluorocarbene Complexes. Organometallics 2013, 32 (1) , 12-15. https://doi.org/10.1021/om3010959
    8. Jian Yuan, Russell P. Hughes, and Arnold L. Rheingold . Unexpected Synthesis of a Perfluoroacyl Complex, Cp*Ir(CO)(COC6F11)Br, by Direct Fluoroalkylation of a CO Ligand, and Elimination of Perfluorocyclohexene by Activation of a γ-C−F Bond. Organometallics 2011, 30 (6) , 1744-1746. https://doi.org/10.1021/om200019d
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    10. Hui Huang, Russell P. Hughes and Arnold L. Rheingold . Synthesis and Structural Characterization of New Perfluoroacyl and Perfluoroalkyl Group 6 Transition Metal Compounds. Organometallics 2010, 29 (8) , 1948-1955. https://doi.org/10.1021/om1001183
    11. Lu Wang, Chengxian Hu, Xue Yang, Ying Fu, Zhengyin Du. Pd‐Catalyzed Synthesis of Aryl Esters Involving Difluorocarbene Transfer Carbonylation. European Journal of Organic Chemistry 2024, 27 (10) https://doi.org/10.1002/ejoc.202400032
    12. Xue Ding, Yu-Fei Yao, Weikang Lin, Zhengqing Ye, Cheng-Pan Zhang. Group VIII metal difluorocarbene complexes: Synthesis and applications. Journal of Fluorine Chemistry 2024, 273 , 110238. https://doi.org/10.1016/j.jfluchem.2023.110238
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    14. Xue‐Ying Zhang, Shi‐Ping Sun, Yue‐Qian Sang, Xiao‐Song Xue, Qiao‐Qiao Min, Xingang Zhang. Reductive Catalytic Difluorocarbene Transfer via Palladium Catalysis. Angewandte Chemie 2023, 135 (37) https://doi.org/10.1002/ange.202306501
    15. Xin Zeng, Yao Li, Qiao-Qiao Min, Xiao-Song Xue, Xingang Zhang. Copper-catalysed difluorocarbene transfer enables modular synthesis. Nature Chemistry 2023, 15 (8) , 1064-1073. https://doi.org/10.1038/s41557-023-01236-8
    16. Richard A. Manzano, Anthony F. Hill. Fluorocarbyne complexes via electrophilic fluorination of carbido ligands. Chemical Science 2023, 14 (14) , 3776-3781. https://doi.org/10.1039/D3SC00261F
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    18. Kai Wu, Xuyang Zhang, Liang‐Liang Wu, Jie‐Sheng Huang, Chi‐Ming Che. A Convergent, Modular Approach to Trifluoromethyl‐Bearing 5‐Membered Rings via Catalytic C(sp 3 )−H Activation. Angewandte Chemie International Edition 2023, 62 (9) https://doi.org/10.1002/anie.202215891
    19. Chris Douvris, David Matatov, Derek Bussan, Christos Lampropoulos, Donald J. Wink. Synthesis, Characterization, and X-ray Crystallography, of the First Cyclohexadienyl Trifluoromethyl Metal Complex (η5-C6H7)Fe(CO)2CF3. Molecules 2022, 27 (21) , 7595. https://doi.org/10.3390/molecules27217595
    20. Mathilde Rigoulet, David Vesseur, Karinne Miqueu, Didier Bourissou. Gold(I) α‐Trifluoromethyl Carbenes: Synthesis, Characterization and Reactivity Studies. Angewandte Chemie 2022, 134 (25) https://doi.org/10.1002/ange.202204781
    21. Mathilde Rigoulet, David Vesseur, Karinne Miqueu, Didier Bourissou. Gold(I) α‐Trifluoromethyl Carbenes: Synthesis, Characterization and Reactivity Studies. Angewandte Chemie International Edition 2022, 61 (25) https://doi.org/10.1002/anie.202204781
    22. Wei Zhou, Wen-Jie Pan, Jie Chen, Min Zhang, Jin-Hong Lin, Weiguo Cao, Ji-Chang Xiao. Transition-metal difluorocarbene complexes. Chemical Communications 2021, 57 (74) , 9316-9329. https://doi.org/10.1039/D1CC04029D
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    29. Alexander G. Tskhovrebov, Julia B. Lingnau, Alois Fürstner. Gold Difluorocarbenoid Complexes: Spectroscopic and Chemical Profiling. Angewandte Chemie International Edition 2019, 58 (26) , 8834-8838. https://doi.org/10.1002/anie.201903957
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    31. Daniel J. Harrison, Alex L. Daniels, Jia Guan, Bulat M. Gabidullin, Michael B. Hall, R. Tom Baker. Nickel Fluorocarbene Metathesis with Fluoroalkenes. Angewandte Chemie International Edition 2018, 57 (20) , 5772-5776. https://doi.org/10.1002/anie.201802090
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    35. Jian Yuan, Russell P. Hughes, Arnold L. Rheingold. A (pentafluoroethyl)(trifluoromethyl)carbene complex of iridium and reductive activation of its sp 3 α, β, and γ carbon–fluorine bonds to give perfluoro-2-butyne, perfluoro-1,2,3-butatriene and perfluoro-1-irida-2-methyl-2-cyclobutene) complexes. Dalton Transactions 2015, 44 (45) , 19518-19527. https://doi.org/10.1039/C5DT02075A
    36. Jian Yuan, Cheryl J. Bourgeois, Arnold L. Rheingold, Russell P. Hughes. Synthesis, structure, and reactivity of iridium perfluorocarbene complexes: regio- and stereo-specific addition of HCl across a metal carbon double bond. Dalton Transactions 2015, 44 (45) , 19528-19542. https://doi.org/10.1039/C5DT02275D
    37. Graham M. Lee, Daniel J. Harrison, Ilia Korobkov, R. Tom Baker. Stepwise addition of difluorocarbene to a transition metal centre. Chem. Commun. 2014, 50 (9) , 1128-1130. https://doi.org/10.1039/C3CC48468H
    38. Jason Hackenberg, Karsten Krogh‐Jespersen, Alan S. Goldman. Activation of C–O and C–F Bonds by Pincer–Iridium Complexes. 2013, 39-57. https://doi.org/10.1002/9781118742952.ch4
    39. Sonia Martínez‐Salvador, Juan Forniés, Antonio Martín, Babil Menjón, Isabel Usón. Stepwise Degradation of Trifluoromethyl Platinum(II) Compounds. Chemistry – A European Journal 2013, 19 (1) , 324-337. https://doi.org/10.1002/chem.201202648
    40. M. Angeles García‐Monforte, Sonia Martínez‐Salvador, Babil Menjón. The Trifluoromethyl Group in Transition Metal Chemistry. European Journal of Inorganic Chemistry 2012, 2012 (31) , 4945-4966. https://doi.org/10.1002/ejic.201200620
    41. Jongwook Choi, David Y. Wang, Sabuj Kundu, Yuriy Choliy, Thomas J. Emge, Karsten Krogh-Jespersen, Alan S. Goldman. Net Oxidative Addition of C(sp 3 )-F Bonds to Iridium via Initial C-H Bond Activation. Science 2011, 332 (6037) , 1545-1548. https://doi.org/10.1126/science.1200514
    42. Thomas Braun, Falk Wehmeier. C–F Bond Activation of Highly Fluorinated Molecules at Rhodium: From Model Reactions to Catalysis. European Journal of Inorganic Chemistry 2011, 2011 (5) , 613-625. https://doi.org/10.1002/ejic.201001184
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    44. Jian Yuan, Russell P. Hughes, Arnold L. Rheingold. Synthesis and crystallographic characterization of dimeric perfluoroalkyl iridium complexes: [Cp∗Ir(X)(RF)]2 (X = I, RF= CF3, CF2CF3, CF2CF2CF3, CF(CF3)2, CF(CF3)(CF2CF3); X = Cl and Br, RF= CF2CF3), and a new perfluoroethylidene complex Cp∗Ir(PPh3)(CFCF3). Inorganica Chimica Acta 2010, 364 (1) , 96-101. https://doi.org/10.1016/j.ica.2010.06.006
    45. Russell P. Hughes. Fluorine as a ligand substituent in organometallic chemistry: A second chance and a second research career. Journal of Fluorine Chemistry 2010, 131 (11) , 1059-1070. https://doi.org/10.1016/j.jfluchem.2010.06.014
    46. Sonia Martínez‐Salvador, Babil Menjón, Juan Forniés, Antonio Martín, Isabel Usón. Trapping a Difluorocarbene–Platinum Fragment by Base Coordination. Angewandte Chemie 2010, 122 (25) , 4382-4385. https://doi.org/10.1002/ange.200907031
    47. Sonia Martínez‐Salvador, Babil Menjón, Juan Forniés, Antonio Martín, Isabel Usón. Trapping a Difluorocarbene–Platinum Fragment by Base Coordination. Angewandte Chemie International Edition 2010, 49 (25) , 4286-4289. https://doi.org/10.1002/anie.200907031
    48. Russell P. Hughes. Conversion of Carbon–Fluorine Bonds α to Transition Metal Centers to Carbon–Hydrogen, Carbon–Carbon, and Carbon–Heteroatom Bonds. European Journal of Inorganic Chemistry 2009, 2009 (31) , 4591-4606. https://doi.org/10.1002/ejic.200900816
    49. José Vicente, Juan Gil-Rubio, Juan Guerrero-Leal, Delia Bautista. Synthesis of rhodium(i) and rhodium(iii) perfluoroalkyl complexes from [Rh(μ-OH)(COD)]2. Dalton Transactions 2009, 94 (19) , 3854. https://doi.org/10.1039/b822738a
    50. Jian Yuan, Russell P. Hughes, Arnold L. Rheingold. The First Example of a Bis(trifluoromethyl)carbene Transition‐Metal Complex and Its Reduction to a Perfluoroallene Complex. European Journal of Inorganic Chemistry 2007, 2007 (30) , 4723-4725. https://doi.org/10.1002/ejic.200700814
    51. James W. Herndon. The chemistry of the carbon–transition metal double and triple bond: Annual survey covering the year 2005. Coordination Chemistry Reviews 2007, 251 (9-10) , 1158-1258. https://doi.org/10.1016/j.ccr.2006.11.002
    52. R.N. Perutz, T. Braun. Transition Metal-mediated C–F Bond Activation. 2007, 725-758. https://doi.org/10.1016/B0-08-045047-4/00028-5
    53. Hansjörg Himmel, Axel Schulz, Gunther Knör, Nicolai Lehnert. Anorganische Chemie 2005. Nachrichten aus der Chemie 2006, 54 (3) , 214-233. https://doi.org/10.1002/nadc.20060540306
    54. Nicholas C. Fletcher. Noble metals. Annual Reports Section "A" (Inorganic Chemistry) 2006, 102 , 274. https://doi.org/10.1039/b514840p

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