Ligand-controlled synthesis, reactivity and oxo-transfer kinetics of oxomolybdenum-(VI) and -(IV) complexes

Bhattacharjee, Samiran; Bhattacharyya, Ramgopal

doi:10.1039/dt9930001151

Cited by 36 publications

(23 citation statements)

References 17 publications

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“…They are common for structures with the cis-[MoO 2 ]unit in the range of 1.66 Å-1.76 Å [8]. The bond lengths of Mo-O alkoxy of 1.926(2) Åand 1.922(2) Å,are consistent with molybdenum (VI)alkoxide interactions [9,10]. The Mo-Ndistance of 2.292(2) Åis long asa consequence of the strong trans influence of anoxo ligand (O3).…”

Section: Discussionsupporting

confidence: 50%

Crystal structure of dimethylformamide-diethanolateamine-dioxo-molybdenum( VI), MoO2[O(CH2)2NH(CH2)2O][(CH3)2NCHO]

Zhang¹,

Schulzke²,

Schmidt³

et al. 2007

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of material Experimental detailsHydrogen atoms were attached atidealized positions on carbon atoms with U iso related to the U eq of the parent atoms and were refined with the riding model. H100 bound to secondary amine nitrogen N1wasfound and refined freely. DiscussionDiethanolateamine is awell-known and widelyused ligand system and its dioxomolybdenum compound hasbeen studied thoroughly [1]. Toour surprise no crystalstructure of this complex or any related molybdenum diethanolateamine complex wasp ublished so faralthough severalcomplexes of this ligand with other transition and main group metals are structurally characterized [2][3][4][5][6][7].The title complex consists of adiscretem ononuclearu nit, in which the diethanolateamine is coordinated to the molybdenum atom asatridentate ligand to form two five-memberedrings. Two oxo ligands coordinate to the metalt of orm astable cis-dioxomolybdenum(VI)core. ADMFmolecule trans to one oxo group completes the distorted octahedralcoordination sphere. Again this is in the range of analogous complexes with the MoO 2 2+ core (2.28 Å-2.50 Å) [11]. The length of the Mo-O5 bond is 2.438(2) Åwhich is rather long, implying avery weak bonding interaction between the molybdenum and the DMFmolecule. This coordination nevertheless allows to obtain astable distorted octahedralenvironment. The Mo-O(DMF)distance is longer thanMo-Odistances formed by other solvent molecules e.g. MeOH with 2.289 Å-2.385 Å [8,12] or H 2 Owith2.255 Å-2.293 Å [13]. The comparably weakb onding interaction indicates thatDMFis particularly easy to remove from the molecule. The most evident distortionsofthe structure from the idealized octahedralenvironment are defined by the N1-Mo-O1(75.81(7)°), N1-Mo-O2( 74.97(7)°) and O1-Mo-O2( 146.43(7)°) angles. With the strain of two five-memberedchelate rings, two alkoxy groups are bent towards the nitrogen atom.

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Section: Discussionsupporting

confidence: 50%

Crystal structure of dimethylformamide-diethanolateamine-dioxo-molybdenum( VI), MoO2[O(CH2)2NH(CH2)2O][(CH3)2NCHO]

Zhang¹,

Schulzke²,

Schmidt³

et al. 2007

Zeitschrift Für Kristallographie - New Crystal Structures

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“…The numerous molybdenum(VI) Schiff base complexes have been extensively investigated for over twenty years. Owing to their importance in the domains of stereochemistry and structural and analytical chemistry and as model systems for the interaction of organic substrates with catalytic oxide surfaces, some of them are also interesting due to their ability to oxidize thiols, hydrazines, polyketones and tertiary phosphines . Their oxygen atom transfer properties play a significant role in investigating the functioning mechanism of molybdenum oxotransferase .…”

Section: Dioxygen Coordinationmentioning

confidence: 99%

Synthesis and antioxidant activities of Schiff bases and their complexes: a review

Zoubi

Al‐Hamdani

Kaseem

2016

Applied Organom Chemis

202

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Schiff bases, named after https://en.wikipedia.org/wiki/Hugo_Schiff, are aldehyde‐ or ketone‐like compounds in which the carbonyl group is replaced by imine or azomethine group. They are widely used for industrial purposes and also have a broad range of applications as antioxidants. An overview of antioxidant applications of Schiff bases and their complexes is discussed in this review. A brief history of the synthesis and reactivity of Schiff bases and their complexes is presented. Factors of antioxidants are illustrated and discussed. Copyright © 2016 John Wiley & Sons, Ltd.

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“…The reaction system exhibits saturation kinetics at high substrate concentration (Figure 6a), as generally observed for enzyme reaction. Under these conditions, the reaction is first order in (2), as shown by linear plots of log(A t À A a ) versus time, from which the observed rate constants were evaluated [39][40][41]. Similar kinetic behaviour has been observed for oxygen atom transfer reaction of different Mo(IV) complexes with Me 2 SO [40,41].…”

Section: Resultsmentioning

confidence: 73%

“…Under these conditions, the reaction is first order in (2), as shown by linear plots of log(A t À A a ) versus time, from which the observed rate constants were evaluated [39][40][41]. Similar kinetic behaviour has been observed for oxygen atom transfer reaction of different Mo(IV) complexes with Me 2 SO [40,41]. This is in contrast with the second order rate law with a straight line plot of k obs versus [Me 2 SO], as reported by Enemark and coworkers for a mixed ligand Mo(IV) complex [42].…”

Section: Resultsmentioning

confidence: 99%

Studies on a New Binuclear Tungsten(IV)-pterin Complex Showing Reactivity Towards Trimethylamine N-oxide

Sen

Roy

2005

Transition Met Chem

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The new compound [W IV 2 OCl 2 L 2 ] AE DMF (2) has been synthesized by a redox reaction between WOCl 4 and 2-pivaloylamino-6-acetonylisoxanthopterin (H 2 L, 1) in DMF medium. It bas been characterized by elemental analysis, spectroscopy and electrochemistry. Its reactivity towards Me 3 N ! O has been followed both kinetically and stoichiometrically. The reaction follows substrate saturation kinetics and a large negative entropy of activation value points towards involvement of an associative mechanism.

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Ligand-controlled synthesis, reactivity and oxo-transfer kinetics of oxomolybdenum-(VI) and -(IV) complexes

Cited by 36 publications

References 17 publications

Crystal structure of dimethylformamide-diethanolateamine-dioxo-molybdenum( VI), MoO2[O(CH2)2NH(CH2)2O][(CH3)2NCHO]

Crystal structure of dimethylformamide-diethanolateamine-dioxo-molybdenum( VI), MoO2[O(CH2)2NH(CH2)2O][(CH3)2NCHO]

Synthesis and antioxidant activities of Schiff bases and their complexes: a review

Studies on a New Binuclear Tungsten(IV)-pterin Complex Showing Reactivity Towards Trimethylamine N-oxide

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