Complexation of Molybdenum(V) with Glycolic Acid: An Unusual Orientation of Glycolato Ligand in {Mo2O4}2+ Complexes

Modec, Barbara; Dolenc, Darko; Kasunič, Marta

doi:10.1021/ic7020726

Cited by 42 publications

(25 citation statements)

References 56 publications

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“…The negative ion ESI mass spectrum exhibited a group of peaks centered at m/z 440 with an isotopic pattern characteristic of a polynuclear Mo complex containing Cl, in particular a doubly charged tetranuclear complex. For example, the pattern agreed well with that calculated for [Mo 41 In the FT-IR spectra of these compounds, strong bands are usually present at 950-980 for n(MoQO) and 660-760 cm À1 for n(Mo-O-Mo), similar to those observed in this work for the recovered solids. The rhombic tetranuclear core may be regarded as a fusion of two {Mo 2 O 4 } 2+ units sharing a pair of triply-bridging oxo groups and a pair of doubly-bridging OR groups.…”

Section: Characterisation Studiessupporting

confidence: 89%

Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of α-pinene oxide to campholenic aldehyde

et al. 2014

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The complex [{(Z 5 -Ind)Mo(CO) 2 (m-Cl)} 2 ] (1) has been tested for the industrially relevant catalytic isomerisation of a-pinene oxide (PinOx) to campholenic aldehyde (CPA) in the liquid phase. PinOx conversion and CPA selectivity are strongly influenced by the solvent employed. Complete conversion of PinOx was achieved within 1 min at 55 1C or 30 min at 35 1C using 1,2-dichloroethane as solvent, giving CPA in 68% yield.Other products included trans-carveol, iso-pinocamphone and trans-pinocarveol. The stability of 1 under the reaction conditions used was investigated by using FT-IR spectroscopy and electrospray ionisation mass spectrometry (ESI-MS) to characterise recovered solids. In the presence of air/moisture 1 undergoes oxidative decarbonylation upon dissolution to give oxomolybdenum species that are proposed to include a tetranuclear oxomolybdenum(V) complex. Conversely, ESI-MS studies of 1 dissolved in dry acetonitrile show mononuclear species of the type [IndMo(CO) 2 (CH 3 CN) n ] + . The crystal structure of the ring-slipped dicarbonyl complex [(Z 3 -Ind)Mo(CO) 2 Cl(CH 3 CN) 2 ] (2) (obtained after dissolution of 1 in acetonitrile) is reported.

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Section: Characterisation Studiessupporting

confidence: 89%

Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of α-pinene oxide to campholenic aldehyde

et al. 2014

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“…19 Similar situations can be found in coordination compounds where the MPW1K functional has already found applications. 20 It has also proved to be more accurate than B3LYP in CT complexes. 21 Calculation at the MP2 level does not result in significant improvement in the calculated distances.…”

Section: Solid-state Structuresmentioning

confidence: 99%

EDA Complexes of N-halosaccharins with N- and O-donor ligands

Dolenc

Modec

2009

New J. Chem.

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A series of EDA complexes of N-iodosaccharin (NISac) and N-bromosaccharin (NBSac) with nitrogen and oxygen electron-pair donors, NISacÁH 2 O, NISacÁTHF, NISacÁPy, NISac 2 ÁPyz and NBSac 2 ÁPyz, was prepared and examined by X-ray diffraction and NMR. The complexes are relatively stable, crystalline compounds with the ligand bound to the halogen atom in a nearly linear arrangement N-halogen-ligand. The halogen-ligand distances are inversely proportional to the donor ability of the ligand. The interactions between ligand and halogen are stronger for iodine than bromine. The X-ray structure analysis has shown that for some compounds the N-X bond in the halosaccharin moiety is not coplanar with the isothiazole ring, and the quantum-chemical calculations demonstrate a high flexibility of the corresponding angle. Complexes were modelled also by DFT calculations using B3LYP and MPW1K functionals. A better fit of the computed geometry was obtained by the geometry optimization in a polar solvent continuum than in vacuum.

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“…Other Lewis acidic centers that form complexes with alpha hydroxy carboxylic acids include: Mo(V) which forms both monodentate complexes with HOCH2COO -and bidentate chelated complexes containing the -OCH2COO -entity [23], VO2 2+ , with the bidentate -OCH2COO -ligand, and VO 4+ , with both chelating bidentate -OCH2COOligand and mondentate HOCH2COO - [24], peroxovandium(V), with bidentate glycolic acid [25], oxovanadium(IV) with bidentate alphahydroxy carboxylic acid [26], and 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 18 the diethyltin(II) cation with both alpha hydroxy-and thiohydroxy carboxylic acids, [27]. A variety of metal ions have also functioned as the Lewis acid for complexation with alpha-hydroxy carboxylic acids: Cu(II) with mondentate, bidentate chelating, and the neutral carboxylic acid [28], Mn(II) with glycolic and lactic acids, as well as other acid bidentate anions [29], Ag(I) with monodentate glycolate [30], La(III), Ce(III), and Nd(III) with both bidentate chelating and monodentate chelating glycolate [31], Cm(III) and Cu(III) with mostly monodentate glycolate [32], and Th(IV) and a variety of lanthanides(III) with mostly monodentate glycolate [33].…”

Section: Structural Effects In Alphahydroxy Molybdate Complexesmentioning

confidence: 99%

95Mo NMR study of the effect of structure on complexation of molybdate with alpha and beta hydroxy carboxylic acid ligands

2016

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95 MoNMR study of the effect of structure on complexation of molybdate with alpha and beta hydroxy carboxylic acid ligands Abstract The utility of the quadrupolar, spin 5/2 95 Mo nucleus in NMR studies of complexation of molybdate have been demonstrated using model alpha hydroxyl carboxylic acids. The 95 Mo NMR spectra show a down field shift of the resonance upon complexation, presumably due to the smaller 1/∆E paramagnetic shift term for the octahedral molybdate complexes relative to the tetrahedral molybdate ion.The 95 Mo resonances are sufficiently distinct to establish three solution complexes for the reaction of lactic acid with molybdate. The effect of the structure of hydroxy carboxylic acids on complexation to molybdate (MoO4 2-) was studied with 13 C and 95 Mo NMR spectroscopy. The use of the NMR spectra of both nuclei © 2015. This manuscript version is made available under the Elsevier user license allows monitoring of the Lewis acidic molybdate site and the Lewis basic ligands.The beta hydroxy carboxylic acids, 3-hydroxypropanoic acid and salicylic acid,did not form complexes with molybdate, suggesting a preference for 5-membered chelated rings. The Lewis acidity of the negatively charged molybdate ion is rationalized with two schemes for the reaction with the chelating bidentate alphahydroxyl carboxylic acids.

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Complexation of Molybdenum(V) with Glycolic Acid: An Unusual Orientation of Glycolato Ligand in {Mo₂O₄}²⁺ Complexes

Cited by 42 publications

References 56 publications

Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of α-pinene oxide to campholenic aldehyde

Application of an indenyl molybdenum dicarbonyl complex in the isomerisation of α-pinene oxide to campholenic aldehyde

EDA Complexes of N-halosaccharins with N- and O-donor ligands

95Mo NMR study of the effect of structure on complexation of molybdate with alpha and beta hydroxy carboxylic acid ligands

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