Carbon−Nitrogen Bond Formation via the Reaction of Terminal Alkynes with a Dinuclear Side-on Dinitrogen Complex
- 16 July 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (31), 9480-9481
- https://doi.org/10.1021/ja049490b
Abstract
The dinuclear dinitrogen complex ([P2N2]Zr)2(μ-η2:η2-N2) reacts with terminal aryl alkynes to generate a new species in which the dinitrogen unit has been functionalized. The products formed have the general formula ([P2N2]Zr)2(μ-η2:η2-N2CCAr)(μ-CCAr) and display a styryl−hydrazido unit bridging the two Zr centers along with a bridging arylalkynide. The crystal structures of three of these products are reported. A mechanism is proposed for this process that involves cycloaddition of the alkyne to the side-on dinitrogen unit followed by protonation of the Zr−C bond by a second equivalent of terminal alkyne. A fluxional process is operative in solution that equilibrates the phosphorus nuclei at high temperature; in the slow exchange limit, the two [P2N2]Zr ends of complex are inequivalent as evidenced by four resonances in the 31P NMR spectrum for the inequivalent phosphorus donors. This C−N bond-forming reaction is unique in that an activated dinitrogen fragment undergoes a reaction with an alkyne.Keywords
This publication has 13 references indexed in Scilit:
- Dinitrogen Coordination Chemistry: On the Biomimetic BorderlandsChemical Reviews, 2004
- Reduction of Dinitrogen to Planar Bimetallic M2(μ-η2:η2-N2) Complexes of Y, Ho, Tm, and Lu Using the K/Ln[N(SiMe3)2]3 Reduction SystemJournal of the American Chemical Society, 2003
- Anti-Markovnikov Intermolecular Hydroamination: A Bis(amidate) Titanium Precatalyst for the Preparation of Reactive AldiminesOrganic Letters, 2003
- Activation of Molecular Nitrogen: Coordination, Cleavage and Functionalization of N2 Mediated By Metal ComplexesAdvanced Synthesis & Catalysis, 2003
- Cyclopentadienyl Substituent Effects on Reductive Elimination Reactions in Group 4 Metallocenes: Kinetics, Mechanism, and Application to Dinitrogen ActivationJournal of the American Chemical Society, 2003
- Activation and functionalization of molecular nitrogen by metal complexesThe Chemical Record, 2003
- Cycloaddition Reactions of the Titanium Imide [Ti(NBut){MeC(2-C5H4N)(CH2NSiMe3)2}(py)] with ButCP and MeCNOrganometallics, 2000
- Transformation of Coordinated Dinitrogen by Reaction with Dihydrogen and Primary SilanesScience, 1997
- Synthesis of Heterocycles Utilizing N2-TiCl4-Li-TMSClThe Journal of Organic Chemistry, 1995
- Preparation and properties of molybdenum and tungsten dinitrogen complexes. 25. Catalytic conversion of molecular nitrogen into silylamines using molybdenum and tungsten dinitrogen complexesJournal of the American Chemical Society, 1989