Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex

@article{Laplaza1995DinitrogenCB,
  title={Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex},
  author={Catalina E. Laplaza and Christopher C. Cummins},
  journal={Science},
  year={1995},
  volume={268},
  pages={861 - 863}
}
Cleavage of the relatively inert dinitrogen (N2) molecule, with its extremely strong N≡N triple bond, has represented a major challenge to the development of N2 chemistry. This report describes the reductive cleavage of N2 to two nitrido (N3–) ligands in its reaction with Mo(NRAr)3, where R is C(CD3)2CH3 and Ar is 3,5-C6H3(CH3)2', a synthetic three-coordinate molybdenum(III) complex of known structure. The formation of an intermediate complex was observed spectroscopically, and its conversion… Expand
View on AAAS
ncbi.nlm.nih.gov
342 Citations

Topics from this paper

      342 Citations

      Citation Type

      Citation Type

      Achieving C-N bond cleavage in dinuclear metal cyanide complexes.
      TLDR
      An important conclusion from this work is that a successful strategy for achieving cleavage of multiply-bonded, and relatively unreactive, molecular fragments, may simply lie in tuning the electronic structures and orbital interactions by judicious choice of metal sites and ligand groups. Expand
      Dinitrogen activation upon reduction of a triiron(II) complex.
      TLDR
      IR and Mössbauer spectroscopy, and elemental analysis on 2 and 2-1 as well as the tri(amido)tri iron(II) 3 and tri(methoxo)triiron 4 congeners support the assignment of the reduction product as containing protonated N-atom bridges. Expand
      Sulfur dioxide activation: a theoretical investigation into dual S═O bond cleavage by three-coordinate molybdenum(III) complexes.
      TLDR
      This theoretical study investigates a mechanism for this SO2 cleavage reaction that is mediated by MoL3 and indicates that an electron transfers into the SO2 ligand, which leads to Mo oxidation and initiates SO2 coordination along the quartet surface. Expand
      Dinitrogen-Molybdenum Complex Induces Dinitrogen Cleavage by One-Electron Oxidation.
      TLDR
      Density-functional theory (DFT) calculations reveal that the unstable monomeric oxidized MoI species is converted into 2 via the dimeric structure involving a zigzag transition state. Expand
      NO2 bond cleavage by MoL3 complexes.
      TLDR
      Direct bond cleavage via an η(1)-O complex is the likely mechanism for the experimental reaction that occurs at ambient temperature and pressure, unlike the other known reactions between MoL3 complexes and small molecules. Expand
      Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen
      TLDR
      The proposed mechanism involves initial adduct formation that facilitates inner-sphere electron transfer to cleave the N-N bond to form a species with bridging nitrides, one of which is transformed by nucleophilic attack of a phosphine donor to generate the observed phosphinimide. Expand
      Facile Dinitrogen and Dioxygen Cleavage by a Uranium(III) Complex: Cooperativity Between the Non-innocent Ligand and the Uranium Center.
      TLDR
      It is established that the combination of uranium and a low-valent nonmetal is a promising strategy to achieve a full N2 and O2 cleavage under ambient conditions, which may aid the design of new system for small molecules activation. Expand
      Activation and cleavage of dinitrogen by three-coordinate metal complexes involving Mo(III) and Nb(II/III).
      TLDR
      It can be concluded that the level of activation of the N-N bond does not necessarily correlate with the ease of cleavage of the dinitrogen bridge. Expand
      Base-catalyzed dinitrogen cleavage by molybdenum amides
      Abstract The amides Mo(NRAr)3 (R=CMe3 or C(CD3)2CH3, Ar=3,5-C6H3Me2) and HMo(η2-Me2CNAr)(NRAr)2 (R=CHMe2 or CH(CD3)2, Ar=3,5-C6H3Me2) are known to effect the six-electron reductive cleavage of… Expand
      Theoretical investigation of the pathway for reductive cleavage of dinitrogen by a vanadium diamidoamine complex
      Density functional calculations show that [HN(CH2CH2NH)2V] will bind N2 in a sideways fashion; further reaction with another molecule of [HN(CH2CH2NH)2V] leads to reductive cleavage of the N2 moiety… Expand
      ...
      1
      2
      3
      4
      5
      ...

      References

      SHOWING 1-10 OF 34 REFERENCES
      End-on versus side-on bonding of dinitrogen to dinuclear early transition-metal complexes
      The preparation of a series of dinuclear complexes of zirconium and tantalum is presented in an effort to determine factors involved in the coordination mode of the bridging dinitrogen ligand.… Expand
      Trialkoxynitridomolybdenum compounds: (RO)3Mo.ident.N. Preparation, structures (R = tert-Bu and iso-Pr), and comparisons with a tungsten analog (R = tert-Bu)
      The compound (t-BuO)/sub 3/Mo identical with N is formed in the reaction between Cl/sub 3/Mo identical with N and LiO-t-Bu (3 equiv) in THF and is obtained as a white crystalline compound by either… Expand
      Intermediate complexes in chemical and biological nitrogen fixation
      Mechanism of dinitrogen reduction in protic media is discussed in the light of results obtained for specially prepared binuclear complexes M"M with bridging dinitrogen capable to be protonated and… Expand
      The nitrogenase FeMo-cofactor and P-cluster pair: 2.2 A resolution structures.
      TLDR
      Findings indicate that a cavity exists in the interior of the FeMo-cofactor that could be involved in substrate binding and suggest that redox reactions at the P-cluster pair may be linked to transitions of two cluster-bound sulfurs between disulfide and sulfide oxidation states. Expand
      Multiple bonds between metal atoms
      Introduction and Survey.- Complexes of the Group 5 Elements.- Chromium Compounds.- Molybdenum Compounds.- Tungsten Compounds.- X3M=MX3 Compounds of Molybdenum and Tungsten.- Technetium Compounds.-… Expand
      15N‐NMR Spectroscopy—New Methods and Applications [New Analytical Methods (28)]
      STERISCH ABGESCHIRMTE NITRIDOKOMPLEXE VON MOLYBDAN UND WOLFRAM DIE KRISTALLSTRUKTUREN VON MON(NPH2)3 UND W4N4(NPH2)6(ONC4H9)2
      Die Umsetzungen von MoNCl3 bzw. WNCl3 mit Lithium-Diphenylamid in Tetrahydrofuran fuhren zu den monomeren Nitridokomplexen MN(NPh2)3 mit KZ = 4 an den Metallatomen. Bei Anwesenheit von… Expand
      Dinitrogen Reduction by Nitrogenase: If N_2 Isn’t Broken, It Can’t be Fixed
      Nitrogenase consists of two component metalloproteins, the iron protein and molybdenum-iron protein, which together catalyze the ATP-dependent reduction of dinitrogen to ammonia during biological… Expand
      Preparation and characterization of two high oxidation state molybdenum dinitrogen complexes: [MoCp*Me3]2(.mu.-N2) and [MoCp*Me3](.mu.-N2)[WCp'Me3]
      (MoCp{sup *}Cl{sub 4}){sub 2} (Cp{sup *} = C{sub 5}Me{sub 5}) is alkylated by MeMgCl in tetrahydrofuran to give red microcrystalline MoCp{sup *}Me{sub 4} in {approximately}70% yield. MoCp{sup… Expand
      Science 260, 792 (1993); D
      • C. Rees, Curr. Opin. Struct. Biol. 3, 921 (1993); W. H. Orme-Johnson, Science 257, 1639 (1992); D. Sellmann, Angew. Chem. Int. Ed. Engl. 32, 64 (1993); H. B. Deng and R. Hoffmann, ibid., p.
      ...
      1
      2
      3
      4
      ...