Halogenation and oxygenation of the metal and oxidation of phosphorus in complexes of the type M(dppe) 2 (N 2 ) 2 (M=Mo, W) by reaction with thionylhalides

Stoll, Carola; Lorenz, Ingo‐Peter; Nöth, Heinrich; Ponikwar, Werner

doi:10.1016/s0022-328x(00)00113-3

Cited by 10 publications

(4 citation statements)

References 12 publications

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“…The Mo centre has a distorted octahedral geometry involving four terminal Cl ligands and a chelating cis ‐CH 2 (CO 2 Me) 2 ligand. A similar geometry was previously found in other MoCl 4 (L–L) complexes containing bidentate ligands 20,24…”

Section: Resultssupporting

confidence: 87%

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

et al. 2013

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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.

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Section: Resultssupporting

confidence: 87%

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

et al. 2013

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“…This situation resembles that previously reported for the analogous complex MoCl 4 (dme) (dme = 1,2-dimethoxyethane) 28 and for MoCl 4 (dppeO 2 ) [dppeO 2 = 1,2-bis(diphenylphosphoryl)ethane]. 29 The room temperature reaction of 1 with MeOCH 2 -CH 2 OCH 2 Cl was accompanied by partial, non-selective The investigation on the reactivity of 1 with diethers was concluded by analyzing the interaction with 1,3-dioxane. No metal products could be isolated and identified in this case, notwithstanding a NMR experiment pointed out the occurrence of non-selective activation (O-Csp 3 bonds) of the organic reactant (Scheme 3).…”

Section: Dalton Transactions Papersupporting

confidence: 88%

The reactivity of molybdenum pentachloride with ethers: routes to the synthesis of MoIVCl4 adducts, Mo(v) chlorido-alkoxides and Mo(v) oxydo-chlorides

2013

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The reactivity of molybdenum pentachloride, 1, with a selection of mono- and diethers was investigated at room temperature in a non-coordinating solvent (dichloromethane). The Mo(IV) complex MoCl4(OMe2)2, 2, was obtained in 75% yield by the reaction of 1 with an excess of Me2O; similarly, MoCl4(κ(2)-L) [L = EtOCH2CH2OEt, 6a; MeOCH2CH(Me)OMe, 6b] were prepared in good yields by 1:1 combination of 1 with the appropriate diether. MoCl5 reacted with OMePh and Et2O affording variable amounts of RCl (R = Me and Et, respectively); MoCl3(OPh)2, 3, was isolated in 60% yield from 1 and OMePh. The reactions of 1 with OMe(t)Bu, O(t)Bu(CH=CH2), MeOCH2CH2OCH2Cl and 1,3-dioxane proceeded with non-selective activation of the organic material. The oxido-complexes Mo2O2Cl4(μ-OMe)2(μ-MeOH), 4, and MoOCl3(MeOH)2, 5, were isolated in modest amounts from 1/OMe(t)Bu, whereas MoOCl3(κ(2)-MeOCH2CH2OCH2Cl), 7, was obtained in 32% yield from 1/MeOCH2CH2OCH2Cl. All of the isolated metal products were characterized by spectroscopic and analytical techniques, and by X-ray diffractometry in the cases of 2, 4, 5, 6b and 7. NMR/GC-MS analyses were carried out in order to outline the fragmentation pathways of the organic reactants.

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“…[17] Only in some cases is in situ oxidation of dppe the source of dppeO 2 . This occurs in copper, [18,19] lead, [20] molybdenum, [21] zinc, [22] nickel, [23] and cobalt [24] complexes. Recently [Ni(acac) 2 (dmpeO 2 )] n dmpeO 2 = ethylenebis(dimethylphosphinedioxide), which is homologous to 2, was prepared using dmpe and Ni(acac) 2 as a starting material.…”

Section: Structures Of 1d Polymers Of Trans-[ni(acac) 2 (μ 2 -Dppe)] mentioning

confidence: 99%

Acetylacetonate and Acetate Complexes of Nickel(II) Catalyse the Air Oxidation of Phosphines

et al. 2020

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The polymeric complex trans‐[Ni(acac)2(µ2‐dppe)]n·2MeCN {1a, dppe = 1,2‐ethylenebis(diphenylphosphine)} is sometimes transiently deposited from the reaction of [Ni(acac)2] with dppe in MeCN prior to its facile onwards air oxidation to final crystallization of a doubly‐oxygenated relative, cis‐[Ni(acac)2(µ2‐dppeO2)]n {2, dppeO2 = 1,2‐ethylenebis(diphenylphosphineoxide)}. A similar unsolvated phase of the initial polymer, trans‐[Ni(acac)2(µ2‐dppe)]n (1b), can be isolated from toluene. The oxidation of dppe by O2 is catalytic and dppeO2 was isolated in close to stoichiometric yields from solutions containing 5 % Ni(acac)2 relative to dppe. The reaction rate slows after a few turnovers due to inhibition by the product. The relative yields of dppeO2 are higher than those from catalytic air oxidation of methyldiphenylphosphine and triphenylphosphine and we speculate that a pathway for this reaction involves a dimetallic cooperativity enabled specifically by dppe.

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Halogenation and oxygenation of the metal and oxidation of phosphorus in complexes of the type M(dppe) 2 (N 2 ) 2 (M=Mo, W) by reaction with thionylhalides

Cited by 10 publications

References 12 publications

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

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

The reactivity of molybdenum pentachloride with ethers: routes to the synthesis of MoIVCl4 adducts, Mo(v) chlorido-alkoxides and Mo(v) oxydo-chlorides

Acetylacetonate and Acetate Complexes of Nickel(II) Catalyse the Air Oxidation of Phosphines

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