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Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain
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Novel organophosphorus ligands are formed in the reactions of the title complex with alkynes, organic azides, and diazoalkanes. Coupling of the entering. VLC media player is a free and open source cross-platform multimedia player that plays most multimedia files as well as discs, devices, and network streaming.

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Abstract

The phosphinidene-bridged complex [Fe2Cp2(μ-PCy)(μ-CO)(CO)2] (1) reacts with HC≡CR (R = p-tol, CO2Me) to give products incorporating one or two alkyne molecules and involving further coupling with Cp or CO ligands, as shown by the formation of the complexes [Fe2Cp{μ-η5:κ1-C5H4PCyCHCH(p-tol)}(CO)3], [Fe2Cp2{μ-κ1:κ1,η1-CyPCHC(p-tol)C(O)}(μ-CO)(CO)], and [Fe2Cp2(μ-CO)2(CO){PCy(CHCHCO2Me)(C2CO2Me)}]. In contrast, the reactions of 1 with benzyl azide or (trimethylsilyl)diazomethane initially give the simple 1:1 adducts [Fe2Cp2(μ-CyPN3CH2Ph)(μ-CO)(CO)2] and [Fe2Cp2{μ-CyPN2CH(SiMe3)}(μ-CO)(CO)2], respectively, although the latter rearranges to yield [Fe2Cp2{μ-κ1:κ1,η1-CyPN(SiMe3)NCH}(μ-CO)(CO)] under photolytic conditions.

This article is cited by 11 publications.

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  1. M. Esther García, Daniel García-Vivó, Miguel A. Ruiz, and David Sáez . Divergent Reactivity of a Phosphinidene-Bridged Dimolybdenum Complex Toward 1-Alkynes: P–C, P–H, C–C, and C–H Couplings. Organometallics2017,36 (9) , 1756-1764. DOI: 10.1021/acs.organomet.7b00121.
  2. Isabel G. Albuerne, M. Angeles Alvarez, Inmaculada Amor, M. Esther García, Daniel García-Vivó, and Miguel A. Ruiz . Cycloaddition Reactions of the Phosphinidene-Bridged Complex [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(CO)2(η6-HMes*)] with Diazoalkanes and Other Heterocumulenes. Inorganic Chemistry2016,55 (20) , 10680-10691. DOI: 10.1021/acs.inorgchem.6b01930.
  3. Yingdong Lv, Christos E. Kefalidis, Jiliang Zhou, Laurent Maron, Xuebing Leng, and Yaofeng Chen . Versatile Reactivity of a Four-Coordinate Scandium Phosphinidene Complex: Reduction, Addition, and CO Activation Reactions. Journal of the American Chemical Society2013,135 (39) , 14784-14796. DOI: 10.1021/ja406413d.
  4. M. Angeles Alvarez, M. Esther García, Rocío González, and Miguel A. Ruiz . P–C and C–C Coupling Processes in the Reactions of the Phosphinidene-Bridged Complex [Fe2(η5-C5H5)2(μ-PCy)(μ-CO)(CO)2] with Alkynes. Organometallics2013,32 (16) , 4601-4611. DOI: 10.1021/om4005669.
  5. M. Angeles Alvarez, Inmaculada Amor, M. Esther García, Daniel García-Vivó, Miguel A. Ruiz, and Jaime Suárez . Reactivity of the Phosphinidene-Bridged Complexes [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(η6-1,3,5-C6H3tBu3)(CO)2] and [Mo2Cp2(μ-PH)(η6-1,3,5-C6H3tBu3)(CO)2] toward Alkynes: Multicomponent Reactions in the Presence of Ligands. Organometallics2012,31 (7) , 2749-2763. DOI: 10.1021/om201048s.
  6. M. Angeles Alvarez, M. Esther García, Daniel García-Vivó, Alberto Ramos, and Miguel A. Ruiz . Activation of H–H and H–O Bonds at Phosphorus with Diiron Complexes Bearing Pyramidal Phosphinidene Ligands. Inorganic Chemistry2012,51 (6) , 3698-3706. DOI: 10.1021/ic2026945.
  7. M. Angeles Alvarez, M. Esther García, Rocío González, Alberto Ramos, and Miguel A. Ruiz . Heterometallic Derivatives of [Fe2Cp2(μ-PCy)(μ-CO)(CO)2]: Rational Synthesis of Polynuclear Complexes from Neutral Precursors Having Pyramidal–Phosphinidene Bridges. Inorganic Chemistry2011,50 (16) , 7894-7906. DOI: 10.1021/ic2012342.
  8. M. Angeles Alvarez, M. Esther García, Rocío González, Alberto Ramos, and Miguel A. Ruiz . Synthesis and Decarbonylation Reactions of Diiron Cyclopentadienyl Complexes with Bent-Phosphinidene Bridges. Organometallics2011,30 (5) , 1102-1115. DOI: 10.1021/om101125g.
  9. M. Angeles Alvarez, M. Esther García, Rocío González, and Miguel A. Ruiz. Reactions of the Phosphinidene-Bridged Complexes [Fe2(η5-C5H5)2(μ-PR)(μ-CO)(CO)2] (R = Cy, Ph, 2,4,6-C6H2tBu3) with Diazoalkanes. Formation and Rearrangements of Phosphadiazadiene-Bridged Derivatives†. Organometallics2010,29 (21) , 5140-5153. DOI: 10.1021/om100345e.
  10. M. Angeles Alvarez, Inmaculada Amor, M. Esther García, Daniel García-Vivó, Miguel A. Ruiz, and Jaime Suárez. Structure, Bonding, and Reactivity of Binuclear Complexes Having Asymmetric Trigonal Phosphinidene Bridges: Addition of 16-Electron Metal Carbonyl Fragments to the Dimolybdenum Compounds [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(CO)2L] and [Mo2Cp2(μ-PH)(CO)2L] (L = η6-1,3,5-C6H3tBu3)§. Organometallics2010,29 (19) , 4384-4395. DOI: 10.1021/om100529a.
  11. M. Angeles Alvarez, M. Esther García, Rocío González, Alberto Ramos and Miguel A. Ruiz. Chemical and Structural Effects of Bulkness on Bent-Phosphinidene Bridges: Synthesis and Reactivity of the Diiron Complex [Fe2Cp2{μ-P(2,4,6-C6H2tBu3)}(μ-CO)(CO)2]. Organometallics2010,29 (8) , 1875-1878. DOI: 10.1021/om100137d.