The Reactivity of Molybdenum Pentachloride with Ester Molecules: Ester Activation, Metal Reduction, and Synthesis of 1D Coordination Polymers

Abstract

The reactions of Mo 2 Cl 10 (1) with stoichiometric amounts of a variety of molecules containing the ester functionality in anhydrous noncoordinating solvents afforded metal compounds, which were isolated in the solid state and characterized. The 1:4 molar reactions of 1 with methyl formate (HCO 2 Me), methyl methoxyacetate (MeOCH 2 CO 2 Me) and methyl D,L-lactate [D,L-HOCH(Me)CO 2 Me] gave the dinuclear complex [MoOCl 3 {O=C(H)OMe}] 2 (2) and the mononuclear complexes MoOCl 3 [κ 2 -O=C(OMe)CH 2 OMe] (6a) and MoOCl 3 [κ 2 -O=C(OMe)CH(Me)OH] (6b), respectively. According to NMR/GC-MS analyses, activation of the ester [a] 1371 moiety in part of the organic material took place in distinct cases. The molybdenum(IV) 1D coordination polymers [MoCl 4 -κ 2 -{trans-(CO 2 R)CH=CH(CO 2 R)}] n (R = Me, 3a; R = Et, 3b) were prepared by treatment of 1 with 2 equiv. of alkyl fumarates. In contrast, the mononuclear Mo IV complexes MoCl 4 [κ 2 -CH 2 (CO 2 Me) 2 ] (4) and MoCl 4 [κ 2 -{cis-(CO 2 Me)-CH=CH(CO 2 Me)}] (5) were obtained from 1/CH 2 (CO 2 Me) 2 and 1/cis-maleate, respectively. The molecular structures of 2, 3a, 3b, 4, 6a and 6b were ascertained by X-ray diffraction studies.

A crystallographic and spectroscopic study on the reactions of WCl6 with carbonyl compounds

“…The reaction of 1 with trans-(CO 2 Et)CH=CH(CO Et) resulted in the formation of the W(IV) complex [WCl 4 -κ 2 -{trans-(CO 2 Et)CH=CH(CO 2 Et)}] n , 8b, Scheme 7. The latter compound appears to exist as polymer chain comprising bridging bidentate diester ligands; this feature resembles what found for analogous MoCl 4 derivatives 39 and TiCl 4 -parabenzodiester adducts. 40 Magnetic susceptivity analysis revealed the diamagnetic nature of 8b.…”

Synthesis, properties and structural features of molybdenum(v) oxide trichloride complexes with neutral chalcogenoether ligands

“…The geometries are very similar to those found in [(MoOCl 2 L) 2 (µ-Cl) 2 ] (L = OvC(H)OMe, thf, O = CEt 2 ). [27][28][29] The reaction of MoOCl 3 with TeMe 2 in toluene produced brown [{MoOCl 2 (TeMe 2 )} 2 (µ-Cl) 2 ], which is the first Mo(V) complex with a neutral tellurium donor ligand. Crystals were not obtained from this complex due to poor solubility and limited stability in solution, but spectroscopically it is very similar to the other EMe 2 complexes.…”

A Fourfold Interpenetrated Silver Polymer Constructed from a Tetrakis(4‐pyridyl) Ligand: [Ag(L)] {L = 1,1,2,2‐tetrakis(4‐(pyridin‐4‐yl)phenyl)ethane}

“…A metal-reduction phenomenon is quite rare on polymer formation, but at least one example exists in the literature, in which the Mo metal in the dinuclear compound Mo 2 Cl 10 is formally reduced from Mo 5+ to Mo 4+ when this compound reacts with a diester (trans-(CO 2 R)CH CH(CO 2 R): R Me, Et) to produce a 1D polymer. 16 Polymer 1 was characterized by IR, elemental analysis, photoluminescence, and X-ray diffraction. The characteristic N O stretching peak 17 at 1309 cm −1 in the IR spectrum of AgNO 3 is missing in the IR spectrum of polymer 1, which supports the X-ray crystal structure of the polymer without the counterion (NO 3 − ).…”