A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

doi:10.1021/acs.organomet.6b00108

Title: A Tertiary Carbon–Iron Bond as an Fe ^I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron

Journal Article · Mon May 23 00:00:00 EDT 2016 · Organometallics

DOI: https://doi.org/10.1021/acs.organomet.6b00108 · OSTI ID:1352415

Tondreau, Aaron M. ^[1]; Scott, Brian L. ^[1]; Boncella, James M. ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Chemistry and MPA Divisions

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py)₄FeCl₂. Furthermore, we prepared a series of monoalkylated salts of the type (py)₂FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py)₄FeCl₂ resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane that readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py)₂FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe)₂FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe)₂FeCl₂ gave the reduced Fe(0) nitrogen complex (dmpe)₂Fe(N₂). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.

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Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1352415

Report Number(s):: LA-UR--15-29082

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 11 Vol. 35; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Oligomerisation of Ethylene by Bis(imino)pyridyliron and -cobalt Complexes Britovsek, George J. P.; Mastroianni, Sergio; Solan, Gregory A. Chemistry - A European Journal, Vol. 6, Issue 12 https://doi.org/10.1002/1521-3765(20000616)6:12<2221::AID-CHEM2221>3.0.CO;2-U	journal	June 2000
Tetrapyridino-Ferrous Chloride (Yellow Salt) Baudisch, Oskar; Hartung, Walter H.; Milligan, W. O. Inorganic Syntheses https://doi.org/10.1002/9780470132326.ch64	book	January 1939
Simplifying Iron-Phosphine Catalysts for Cross-Coupling Reactions Bedford, Robin B.; Carter, Emma; Cogswell, Paul M. Angewandte Chemie International Edition, Vol. 52, Issue 4 https://doi.org/10.1002/anie.201207868	journal	December 2012
The use of π-organoiron sandwiches in aromatic chemistry Astruc, Didier Topics in Current Chemistry https://doi.org/10.1007/3-540-54324-4_2	book	January 1992
Cyclopentadienyl-carbon monoxide and related compounds of some transitional metals Piper, T. S.; Cotton, F. A.; Wilkinson, G. Journal of Inorganic and Nuclear Chemistry, Vol. 1, Issue 3 https://doi.org/10.1016/0022-1902(55)80053-X	journal	June 1955
Langlebige α-metallierte methylradikale und deren dimere Hillgärtner, Horst; Neumann, Wilhelm P.; Schulten, Winfried Journal of Organometallic Chemistry, Vol. 201, Issue 1 https://doi.org/10.1016/S0022-328X(00)92576-2	journal	November 1980
Contents of Vol. 637–639 Adams, Richard Journal of Organometallic Chemistry, Vol. 637-639, p. 869-875 https://doi.org/10.1016/S0022-328X(01)01226-8	journal	December 2001
Sodium and potassium derivatives of diphenyl(trimethylsilyl)methane Hill, Michael S.; Hitchcock, Peter B. Journal of Organometallic Chemistry, Vol. 664, Issue 1-2 https://doi.org/10.1016/S0022-328X(02)01982-4	journal	December 2002
A new interpretation of the monomer-dimer equilibrium of triphenylmethyl- and alkylsubstituted-diphenyl methyl-radicals in solution Lankamp, H.; Nauta, W. Th.; MacLean, C. Tetrahedron Letters, Vol. 9, Issue 2 https://doi.org/10.1016/S0040-4039(00)75598-5	journal	January 1968
The dimer of 2-methyl-1,1-diphenylpropyl radicals and its reactivity Beckhaus, Hans-Dieter; Schaetzer, Jürgen; Rüchardt, Christoph Tetrahedron Letters, Vol. 24, Issue 32 https://doi.org/10.1016/S0040-4039(00)86255-3	journal	January 1983
The nature of the active site in bis(imino)pyridine iron ethylene polymerisation catalysts Britovsek, George J. P.; Clentsmith, Guy K. B.; Gibson, Vernon C. Catalysis Communications, Vol. 3, Issue 5 https://doi.org/10.1016/S1566-7367(02)00092-4	journal	May 2002
Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity Crossland, Justin L.; Tyler, David R. Coordination Chemistry Reviews, Vol. 254, Issue 17-18 https://doi.org/10.1016/j.ccr.2010.01.005	journal	September 2010
Nitrogen Fixation Revisited on Iron(0) Dinitrogen Phosphine Complexes Field, Leslie D.; Hazari, Nilay; Li, Hsiu L. Inorganic Chemistry, Vol. 54, Issue 10 https://doi.org/10.1021/acs.inorgchem.5b00211	journal	April 2015
Characterization of an Intermediate in the Ammonia-Forming Reaction of Fe(DMeOPrPE) ₂ N ₂ with Acid (DMeOPrPE = 1,2-[bis(dimethoxypropyl)phosphino]ethane) Balesdent, Chantal G.; Crossland, Justin L.; Regan, Daniel T. Inorganic Chemistry, Vol. 52, Issue 24 https://doi.org/10.1021/ic402081q	journal	November 2013
Singlet .dblharw. quintet spin transitions of iron(II) complexes with a P4Cl2 donor set. X-ray structures of the compound FeCl2(Ph2PCH:CHPPh2)2 and of its acetone solvate at 130 and 295 K Cecconi, F.; Di Vaira, M.; Midollini, S. Inorganic Chemistry, Vol. 20, Issue 10 https://doi.org/10.1021/ic50224a053	journal	October 1981
Exchange of dinitrogen between iron and molybdenum centers and the reduction of dinitrogen bound to iron: implications for the chemistry of nitrogenases Leigh, G. J.; Jimenez-Tenorio, M. Journal of the American Chemical Society, Vol. 113, Issue 15 https://doi.org/10.1021/ja00015a050	journal	July 1991
Sterically hindered free radicals. 18. Stabilization of free radicals by substituents as studied by using triphenylmethyls Neumann, Wilhelm P.; Penenory, Alicia; Stewen, Ulrich Journal of the American Chemical Society, Vol. 111, Issue 15 https://doi.org/10.1021/ja00197a053	journal	July 1989
Trimethylenemethane iron tricarbonyl complexes Ehrlich, Kenneth; Emerson, George F. Journal of the American Chemical Society, Vol. 94, Issue 7 https://doi.org/10.1021/ja00762a045	journal	April 1972
Trimethylenemethaneiron Tricarbonyl Emerson, G. F.; Ehrlich, K.; Giering, W. P. Journal of the American Chemical Society, Vol. 88, Issue 13 https://doi.org/10.1021/ja00965a077	journal	July 1966
An Instance of Trivalent Carbon: Triphenylmethyl. Gomberg, M. Journal of the American Chemical Society, Vol. 22, Issue 11 https://doi.org/10.1021/ja02049a006	journal	November 1900
Bis(imino)pyridine Iron(II) Alkyl Cations for Olefin Polymerization Bouwkamp, Marco W.; Lobkovsky, Emil; Chirik, Paul J. Journal of the American Chemical Society, Vol. 127, Issue 27 https://doi.org/10.1021/ja0524447	journal	June 2005
Reduction of N ₂ to Ammonia and Hydrazine Utilizing H ₂ as the Reductant Gilbertson, John D.; Szymczak, Nathaniel K.; Tyler, David R. Journal of the American Chemical Society, Vol. 127, Issue 29 https://doi.org/10.1021/ja053030g	journal	July 2005
Synthesis and Electronic Structure of Cationic, Neutral, and Anionic Bis(imino)pyridine Iron Alkyl Complexes: Evaluation of Redox Activity in Single-Component Ethylene Polymerization Catalysts Tondreau, Aaron M.; Milsmann, Carsten; Patrick, Andrew D. Journal of the American Chemical Society, Vol. 132, Issue 42 https://doi.org/10.1021/ja106575b	journal	October 2010
Iron(I) in Negishi Cross-Coupling Reactions Adams, Christopher J.; Bedford, Robin B.; Carter, Emma Journal of the American Chemical Society, Vol. 134, Issue 25 https://doi.org/10.1021/ja303250t	journal	June 2012
Redox-Controlled Polymerization of Lactide Catalyzed by Bis(imino)pyridine Iron Bis(alkoxide) Complexes Biernesser, Ashley B.; Li, Bo; Byers, Jeffery A. Journal of the American Chemical Society, Vol. 135, Issue 44 https://doi.org/10.1021/ja407920d	journal	October 2013
Highly Active Iron and Cobalt Catalysts for the Polymerization of Ethylene Small, Brooke L.; Brookhart, Maurice; Bennett, Alison M. A. Journal of the American Chemical Society, Vol. 120, Issue 16 https://doi.org/10.1021/ja9802100	journal	April 1998
Thermodynamics of C−H Activation in Multiple Oxidation States: Comparison of Benzylic C−H Acidities and C−H Bond Dissociation Energies in the Isostructural 16−20-Electron Complexes [Fe ^x (η ⁵ -C ₅ R ₅ )(η ⁶ -arene)] ⁿ , x = 0−IV, R = H or Me, n = −1 to +3 Trujillo, Hernando A.; Casado, Carmen M.; Ruiz, Jaime Journal of the American Chemical Society, Vol. 121, Issue 24 https://doi.org/10.1021/ja984101x	journal	June 1999
Iron and Cobalt Ethylene Polymerization Catalysts Bearing 2,6-Bis(Imino)Pyridyl Ligands: Synthesis, Structures, and Polymerization Studies Britovsek, George J. P.; Bruce, Michael; Gibson, Vernon C. Journal of the American Chemical Society, Vol. 121, Issue 38 https://doi.org/10.1021/ja990449w	journal	September 1999
Living Anionic Polymerization of N -Methacryloylazetidine: Anionic Polymerizability of N,N -Dialkylmethacrylamides Suzuki, Takashi; Kusakabe, Jun-ichi; Kitazawa, Keita Macromolecules, Vol. 43, Issue 1 https://doi.org/10.1021/ma901984d	journal	December 2009
Synthesis and properties of the novel .eta.4-trimethylenemethane compounds [.eta.4-C(CH2)3]Fe(CO)2L (L = tertiary phosphines, tert-butyl isocyanide) Girard, Luc; MacNeil, Joseph H.; Mansour, Adnan Organometallics, Vol. 10, Issue 9 https://doi.org/10.1021/om00055a026	journal	September 1991
2,6-Diiminopyridine Iron(II) Dialkyl Complexes. Interaction with Aluminum Alkyls and Ethylene Polymerization Catalysis Cámpora, Juan; Naz, A. Marcos; Palma, Pilar Organometallics, Vol. 24, Issue 21 https://doi.org/10.1021/om050645d	journal	October 2005
Selective Alkylation of 2,6-Diiminopyridine Ligands by Dialkylmanganese Reagents: A “One-Pot” Synthetic Methodology Cámpora, Juan; Pérez, Carmen M.; Rodríguez-Delgado, Antonio Organometallics, Vol. 26, Issue 4 https://doi.org/10.1021/om0609517	journal	February 2007
Redox Chemistry of Bis(phosphaethenyl)pyridine Iron Complexes Nakajima, Yumiko; Ozawa, Fumiyuki Organometallics, Vol. 31, Issue 5 https://doi.org/10.1021/om201280z	journal	February 2012
Synthesis, Electronic Structure, and Alkene Hydrosilylation Activity of Terpyridine and Bis(imino)pyridine Iron Dialkyl Complexes Tondreau, Aaron M.; Atienza, Crisita Carmen Hojilla; Darmon, Jonathan M. Organometallics, Vol. 31, Issue 13 https://doi.org/10.1021/om3004527	journal	June 2012
Spin Density Distribution in Iron(II) and Cobalt(II) Alkyl Complexes Containing 1,3-Bis(2-pyridylimino)isoindolate Ligands Sauer, Désirée C.; Kruck, Matthias; Wadepohl, Hubert Organometallics, Vol. 32, Issue 3 https://doi.org/10.1021/om301198b	journal	January 2013
Synthesis and Hydrogenation Activity of Iron Dialkyl Complexes with Chiral Bidentate Phosphines Hoyt, Jordan M.; Shevlin, Michael; Margulieux, Grant W. Organometallics, Vol. 33, Issue 20 https://doi.org/10.1021/om500329q	journal	June 2014
Iron Phosphine Catalyzed Cross-Coupling of Tetraorganoborates and Related Group 13 Nucleophiles with Alkyl Halides Bedford, Robin B.; Brenner, Peter B.; Carter, Emma Organometallics, Vol. 33, Issue 20 https://doi.org/10.1021/om500518r	journal	June 2014
Synthesis of Bis(imino)pyridine Iron Di- and Monoalkyl Complexes: Stability Differences between FeCH ₂ SiMe ₃ and FeCH ₂ CMe ₃ Derivatives Fernández, Ignacio; Trovitch, Ryan J.; Lobkovsky, Emil Organometallics, Vol. 27, Issue 1 https://doi.org/10.1021/om700913g	journal	December 2007
Synthesis, structure and reactions of a dinitrogen complex of iron(0), [Fe(N2)(depe)2] (depe = Et2PCH2CH2PEt2) Hirano, Masafumi; Akita, Masatoshi; Morikita, Takashi Journal of the Chemical Society, Dalton Transactions, Issue 19 https://doi.org/10.1039/a702019h	journal	January 1997
Novel olefin polymerization catalysts based on iron and cobalt Britovsek, George J. P.; Gibson, Vernon C.; McTavish, Stuart J. Chemical Communications, Issue 7 https://doi.org/10.1039/a801933i	journal	January 1998
Square planar bis(imino)pyridine iron halide and alkyl complexes Bouwkamp, Marco W.; Bart, Suzanne C.; HawrelakPresent address: Department, Eric J. Chemical Communications, Issue 27 https://doi.org/10.1039/b504063a	journal	January 2005
Paramagnetic hydrido- and chloro-complexes of iron(I) Gargano, Michele; Giannoccaro, P.; Rossi, M. Journal of the Chemical Society, Chemical Communications, Issue 7 https://doi.org/10.1039/c3973000233b	journal	January 1973
Reaction of bis(cyclo-octa-1,5-diene)iron with trimethyl phosphite, phosphorus trifluoride, t-butyl isocyanide, carbon monoxide, and bis-1,2-(diphenylphosphino)ethane; the synthesis of [Fe(N2)(diphos)2] Cable, Robert A.; Green, Michael; Mackenzie, Robert E. Journal of the Chemical Society, Chemical Communications, Issue 7 https://doi.org/10.1039/c3976000270b	journal	January 1976
Isolation of a zerovalent iron dinitrogen complex with 1,2-bis(diethylphosphino)ethane ligands Komiya, Sanshiro; Akita, Masatoshi; Yoza, Akira Journal of the Chemical Society, Chemical Communications, Issue 9 https://doi.org/10.1039/c39930000787	journal	January 1993
Bis[1,2-bis(dimethylphosphino)ethane]dihydrogenhydridoiron(II) tetraphenylborate as a model for the function of nitrogenases Hills, Adrian; Hughes, David L.; Jimenez-Tenorio, Manuel Journal of the Chemical Society, Dalton Transactions, Issue 20 https://doi.org/10.1039/dt9930003041	journal	January 1993
Reduction of dinitrogen bound at an iron(0) centre Hall, David A.; Leigh, G. Jeffery Journal of the Chemical Society, Dalton Transactions, Issue 17 https://doi.org/10.1039/dt9960003539	journal	January 1996
1079. Some hydrido-complexes of iron(II) Chatt, J.; Hayter, R. G. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9610005507	journal	January 1961
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
A short history of SHELX Sheldrick, George M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122 https://doi.org/10.1107/S0108767307043930	journal	December 2007
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015

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Title: A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron

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