Metallo-oxides in nitrogen fixation

Hughes, David L.; Mohammed, Modher Y.; Pickett, Christopher J.

doi:10.1039/c39880001481

Cited by 22 publications

(16 citation statements)

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“…In contrast, the reduction of the complex (Mo IV /Mo III ) occurs in an irreversible oneelectron transfer at )1.34 V vs. fc þ /fc. These data illustrate an increased shift of the reduction potential towards more positive values in comparison with that observed on diazoalkane complexes [16].…”

Section: Electrochemical Studiessupporting

confidence: 52%

“…The complex exhibits two electrochemically reversible one-electron oxidations with a half wave potential at 0.46 and 0.81 V vs. fc þ /fc, and which is positively shifted with respect to trans-[MoF(NNCH 2 )(dppe) 2 ] þ [16]. The dependency of the electron transfer processes involving donating and accepting terminal groups can be evaluated by comparing the E 1=2 values.…”

Section: Electrochemical Studiesmentioning

confidence: 99%

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Synthesis and immobilization of molybdenum complexes in a pillared layered clay

Costa¹,

Silva²,

Raposo³

et al. 2004

Microporous and Mesoporous Materials

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New molecular systems based on donor/acceptor groups connected by p-conjugated bridge, trans-[MoF(NNC 7 H 6 SO 2 )-(Ph 2 PCH 2 CH 2 PPh 2 ) 2 ][BF 4 ], have been synthesized. This complex with nonlinear optical (NLO) applications was immobilized by an adsorption process from liquid phase, in the interlayer of a pillared clay (PILC). The metal complex and the new materials were characterized by thermal analysis (DSC), chemical analysis, surface techniques (XPS), X-ray powder diffraction (XRD), nitrogen adsorption isotherms, spectroscopic methods (NMR, FT-IR and UV/Vis) and electrochemical measurements. The studies of the electrochemical and the spectroscopic properties of the complex show interactions between donor and acceptor groups across the conjugated bridge. The results obtained from the studies using different techniques of analysis confirm that the molybdenum complex was effectively immobilized in the host matrix and this process does not modify the morphology or structure of the PILC upon metal complex loading.

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Section: Electrochemical Studiessupporting

confidence: 52%

Section: Electrochemical Studiesmentioning

confidence: 99%

Synthesis and immobilization of molybdenum complexes in a pillared layered clay

Costa¹,

Silva²,

Raposo³

et al. 2004

Microporous and Mesoporous Materials

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“…[f] Described as reversible in ref. but data were not reported. [g] Reversible; potential measured by CV.…”

Section: Resultssupporting

confidence: 72%

Synthesis, Structure, and Bonding of d³ Molybdenum–Oxo Complexes

2020

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Reduction of d2 metal–oxo ions of the form [MO(PP)2Cl]+ (M=Mo, W; PP=chelating diphosphine) produces d3 MO(PP)2Cl complexes, which include the first isolated examples in group 6. The stability and reactivity of the MO(PP)2Cl compounds are found to depend upon the steric bulk of the phosphine ligands: derivatives with bulky phosphines that shield the oxo ligand are stable enough to be isolated, whereas those with phosphines that leave the oxo ligand exposed are more reactive and observed transiently. Magnetic measurements and DFT calculations on MoO(dppe)2Cl indicate the d3 compounds are low spin with a 2[(dxy)2(π*(MoO))1] configuration. X‐ray crystallographic and vibrational‐spectroscopic studies on d2 and d3 [MoO(dppe)2Cl]0/+ establish that the d3 compound possesses a reduced M−O bond order and significantly longer Mo−O bond, accounting for its greater reactivity. These results indicate that the oxo‐centered reactivity of d3 complexes may be controlled through ligand variation.

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“…The conversion of the [Mo(O)I(prP 4 )] + precursor 3 to the corresponding dinitrogen complex was achieved by electrochemical reduction in the presence of dinitrogen and phenol, following the method of Pickett et al (Scheme , top) 19. The latter reagent was added as a weak acid to induce protonation of the oxido group and subsequent elimination as water.…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of the First Chatt‐Type Bis(dinitrogen)‐Molybdenum(0) Complex with a Tetraphosphane Ligand

et al. 2008

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The first Chatt‐type Mo0 dinitrogen complex with a tetraphosphane ligand has been prepared and characterized by NMR as well as infrared and Raman spectroscopy. Importantly, the employed reaction route allows the stereospecific synthesis of this complex as trans‐[Mo(N2)2(meso‐prP4)] (prP4 = a tetraphos ligand with a central propylene bridge). The stereoselectivity in the reaction course is induced by the oxido‐iodido‐molybdenum(IV) precursor [Mo(O)I(prP4)]+ which directs both phenyl groups of the bridging P atoms of prP4 into a meso configuration. The paper establishes a general strategy to synthesize mononuclear Mo0 dinitrogen and related molybdenum complexes with multidentate phosphane ligands which has not been possible to date. Moreover, the obtained molybdenum tetraphos N2 complex should exhibit a higher thermodynamic stability in the reactions of the Chatt cycle of synthetic nitrogen fixation than the conventional bis(diphos) complexes, due to the linkage of the two diphosphane units by an alkyl bridge. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Metallo-oxides in nitrogen fixation

Cited by 22 publications

References 0 publications

Synthesis and immobilization of molybdenum complexes in a pillared layered clay

Synthesis and immobilization of molybdenum complexes in a pillared layered clay

Synthesis, Structure, and Bonding of d³ Molybdenum–Oxo Complexes

Stereoselective Synthesis of the First Chatt‐Type Bis(dinitrogen)‐Molybdenum(0) Complex with a Tetraphosphane Ligand

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Metallo-oxides in nitrogen fixation

Cited by 22 publications

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Synthesis and immobilization of molybdenum complexes in a pillared layered clay

Synthesis and immobilization of molybdenum complexes in a pillared layered clay

Synthesis, Structure, and Bonding of d3 Molybdenum–Oxo Complexes

Stereoselective Synthesis of the First Chatt‐Type Bis(dinitrogen)‐Molybdenum(0) Complex with a Tetraphosphane Ligand

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Synthesis, Structure, and Bonding of d³ Molybdenum–Oxo Complexes