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Synthesis and Structural Characterization of New Perfluoroacyl and Perfluoroalkyl Group 6 Transition Metal Compounds

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Department of Chemistry, 6128 Burke Laboratories, Dartmouth College, Hanover, New Hampshire 03755
Department of Chemistry, University of California, San Diego, California 92093
*To whom correspondence should be addressed. E-mail: [email protected]
Cite this: Organometallics 2010, 29, 8, 1948–1955
Publication Date (Web):March 19, 2010
https://doi.org/10.1021/om1001183
Copyright © 2010 American Chemical Society
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Abstract

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A series of perfluoroacyl group 6 transition metal complexes Cp*M(CO)3[C(O)RF] and CpM(CO)3[C(O)RF] (M = Cr, Mo, W; RF = CF3, CF2CF3, CF2CF2CF3) have been synthesized by treatment of M(CO)6 with Cp*Li or CpNa in DME under reflux, followed by reaction with [RFC(O)]2O at −78 °C. The molecular structures of Cp*M(CO)3[C(O)CF3] (M = Cr, Mo, W) and Cp*Mo(CO)3[C(O)RF] (RF = CF2CF3, CF2CF2CF3) have been determined crystallographically. The chromium and molybdenum perfluoroacyl complexes were readily converted to the corresponding perfluoroalkyl complexes by heating under N2 in the solid state. The tungsten perfluoroacyl complexes were decarbonylated in refluxing toluene or xylene. The molecular structures of Cp*M(CO)3(CF3) (M = Cr and W) and Cp*Mo(CO)3(RF) (RF = CF2CF3, CF2CF2CF3) have been determined crystallographically. Structural comparisons within these compounds and with previously reported analogues are presented, allowing the first evaluations of the effect of the metal (M = Cr, Mo, W) on the M−CF3 parameters and the effect of fluoroalkyl chain length in Mo−RF (RF = CF3, CF2CF3, and CF2CF2CF3) to be made.

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This article is cited by 13 publications.

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  2. Hui Huang, Arnold L. Rheingold and Russell P. Hughes. Synthesis and X-ray Structure of a Diamagnetic Oxo-Bridged Trifluoromethyl−Chromium(V) Complex: Structural and Computational Comparisons between CF3 and CH3 Ligands in Two Different Oxidation States of Chromium. Organometallics 2010, 29 (16) , 3672-3675. https://doi.org/10.1021/om100543t
  3. Chris Douvris, Christos Lampropoulos, David Matatov, Donald J. Wink, Aleksey E. Kuznetsov, Derek Bussan. Synthesis and structural characterization of the first stable cycloheptatrienyl metal complexes bearing a CF3 moiety. DFT investigations of structures, energetics, NBO charges, and frontier MOs of W-CF3 and Mo-CF3 with η7-C7H7 and η5-C5H5. Polyhedron 2022, 221 , 115875. https://doi.org/10.1016/j.poly.2022.115875
  4. Tingting Song, Ying Mu. Cyclic and Non-cyclic Pi Complexes of Chromium. 2021,,https://doi.org/10.1016/B978-0-12-820206-7.00056-1
  5. Anders Reinholdt, Orion Staples, Daniel J. Mindiola. Chromium(II) Complexes. 2020,,https://doi.org/10.1016/B978-0-08-102688-5.00012-X
  6. Alejandro Portugués, Inmaculada López‐García, Javier Jiménez‐Bernad, Delia Bautista, Juan Gil‐Rubio. Photoinitiated Reactions of Haloperfluorocarbons with Gold(I) Organometallic Complexes: Perfluoroalkyl Gold(I) and Gold(III) Complexes. Chemistry – A European Journal 2019, 25 (68) , 15535-15547. https://doi.org/10.1002/chem.201903058
  7. Hai-Yang Zhao, Zhang Feng, Zhiji Luo, Xingang Zhang. Carbonylation of Difluoroalkyl Bromides Catalyzed by Palladium. Angewandte Chemie 2016, 128 (35) , 10557-10561. https://doi.org/10.1002/ange.201605380
  8. Hai-Yang Zhao, Zhang Feng, Zhiji Luo, Xingang Zhang. Carbonylation of Difluoroalkyl Bromides Catalyzed by Palladium. Angewandte Chemie International Edition 2016, 55 (35) , 10401-10405. https://doi.org/10.1002/anie.201605380
  9. Simone A. Hauser, Robert M. Reich, János Mink, Alexander Pöthig, Mirza Cokoja, Fritz E. Kühn. Influence of structural and electronic properties of organomolybdenum( ii ) complexes of the type [CpMo(CO) 3 R] and [CpMo(O 2 )(O)R] (R = Cl, CH 3 , CF 3 ) on the catalytic olefin epoxidation. Catalysis Science & Technology 2015, 5 (4) , 2282-2289. https://doi.org/10.1039/C4CY01604A
  10. 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
  11. Igor V. Kuvychko, James B. Whitaker, Bryon W. Larson, Travis C. Folsom, Natalia B. Shustova, Stanislav M. Avdoshenko, Yu-Sheng Chen, Hui Wen, Xue-Bin Wang, Lothar Dunsch, Alexey A. Popov, Olga V. Boltalina, Steven H. Strauss. Substituent effects in a series of 1,7-C60(RF)2 compounds (RF = CF3, C2F5, n-C3F7, i-C3F7, n-C4F9, s-C4F9, n-C8F17): electron affinities, reduction potentials and E(LUMO) values are not always correlated. Chemical Science 2012, 3 (5) , 1399. https://doi.org/10.1039/c2sc01133f
  12. Hui Huang, Russell P. Hughes, Arnold L. Rheingold. Synthesis and structural characterization of group 6 transition metal complexes with terminal fluoromethylidyne (CF) ligands; a DFT/NBO/NRT comparison of bonding characteristics of terminal NO, CF and CH ligands. Dalton Trans. 2011, 40 (1) , 47-55. https://doi.org/10.1039/C0DT01006E
  13. 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

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