Methanolysis of MoCl5 in the presence of different alkaline agents; molecular structures of the polynuclear molybdenum(V) methoxides and electron charge density distribution from X-ray diffraction study of the new K–Mo cluster

Bazhenova, T. A.; Kuznetsov, Denis A.; Kovaleva, N. V.; Manakin, Yuri V.; Savinykh, T. A.; Shestakov, Alexander F.

doi:10.1016/j.poly.2014.03.057

Cited by 10 publications

(15 citation statements)

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“…A closely related binuclear molybdenum(V) alkoxide 7 was prepared by salt metathesis between MoCl 5 and NaOMe, but complete ligand exchange could not be accomplished either. 20 , 21 Analogous reactions with electron-rich alkoxides are unlikely in view of the ease of reduction of MoCl 5 even by much milder agents; 22 in any case, no follow-up investigation describing the preparation of analogues of 7 has been published.…”

Section: Introductionmentioning

confidence: 99%

Isolation of a Homoleptic Non-oxo Mo(V) Alkoxide Complex: Synthesis, Structure, and Electronic Properties of Penta-tert-Butoxymolybdenum

et al. 2020

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Treatment of [MoCl 4 (THF) 2 ] with MO t Bu (M = Na, Li) does not result in simple metathetic ligand exchange but entails disproportionation with formation of the well-known dinuclear complex [( t BuO) 3 Mo≡Mo(O t Bu) 3 ] and a new paramagnetic compound, [Mo(O t Bu) 5 ]. This particular five-coordinate species is the first monomeric, homoleptic, all-oxygen-ligated but non-oxo 4d 1 Mo(V) complex known to date; as such, it proves that the dominance of the Mo=O group over (high-valent) molybdenum chemistry can be challenged. [Mo(O t Bu) 5 ] was characterized in detail by a combined experimental/computational approach using X-ray diffraction; UV/vis, MCD, IR, EPR, and NMR spectroscopy; and quantum chemistry. The recorded data confirm a Jahn–Teller distortion of the structure, as befitting a d 1 species, and show that the complex undergoes Berry pseudorotation. The alkoxide ligands render the disproportionation reaction, leading the formation of [Mo(O t Bu) 5 ] to be particularly facile, even though the parent complex [MoCl 4 (THF) 2 ] itself was also found to be intrinsically unstable; remarkably, this substrate converts into a crystalline material, in which the newly formed Mo(III) and Mo(V) products cohabitate the same unit cell.

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Section: Introductionmentioning

confidence: 99%

Isolation of a Homoleptic Non-oxo Mo(V) Alkoxide Complex: Synthesis, Structure, and Electronic Properties of Penta-tert-Butoxymolybdenum

et al. 2020

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“…The reaction of [MoCl 3 (thf) 3 ] with both 6 and 7 in methanol resulted in the formation of a mixture of compounds, including [Mo 2 Cl 4 (OCH 3 ) 4 (CH 3 OH) 2 ] ( 1 ), [Mo 4 Cl 4 O 2 (OCH 3 ) 6 (CH 3 OH) 4 ] ( 4 ), and [Mo 8 O 16 (OCH 3 ) 6 Cl 2 (CH 3 OH) 4 ] (described in ref 26…”

Section: Resultsmentioning

confidence: 63%

“…It is also of interest to make a comparison between 1 and its Mo V analogue, [Mo 2 Cl 4 (OCH 3 ) 6 ] ( 5 ),24b,26 which was obtained in a similar manner to 1 , that is, by methanolysis of molybdenum(V) chloride 26. The Mo ··· Mo distance in 1 is considerably shorter than that in 5 (2.511 vs. 2.732 Å), which suggests the presence of a metal–metal double bond in 1 , as in the case of the tungsten dimer 23.…”

Section: Resultsmentioning

confidence: 96%

“…We were intrigued to examine whether this approach is applicable to the preparation of Mo 3+ ,Mo 4+ clusters starting from the readily available compounds [Mo 3+ Cl 3 (thf) 3 ] and [NaMo 5+ 2 O 2 (OCH 3 ) 7 (CH 3 OH)] ( 6 ),26 [Mo 5+ 2 Cl 2 (OCH 3 ) 8 ] ( 7 ),24a [Mo 5+ 2 Cl 4 (OCH 3 ) 6 ] ( 5 ) 26. Initial efforts in this direction yielded some valuable results, however, their mechanistic interpretation appears not to be straightforward.…”

Section: Resultsmentioning

confidence: 99%

“…MoCl 5 (Aldrich) was used without further purification. ( n Bu) 4 NPF 6 (Aldrich, 98 %) was recrystallized from ethanol and dried in vacuo at 80 °C for 24 h. [Mo 2 Cl 4 (OCH 3 ) 6 ],26 [MoCl 4 (CH 3 CN) 2 ],42 and [MoCl 3 (thf) 3 ]43 were prepared according to published procedures. Methanol was dried by heating at reflux with magnesium methoxide followed by distillation.…”

Section: Methodsmentioning

confidence: 99%

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Developing Pathways to the Synthesis of Low‐Valence Molybdenum Methoxides: Preparation, Characterization, and Redox Chemistry of Dimeric and Tetrameric Molybdenum Alkoxide Clusters

et al. 2015

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The rare Mo=Mo double-bonded dimeric alkoxide complex [Mo 2 Cl 4 (OCH 3 ) 4 (CH 3 OH) 2 ] (1) was prepared by the simple methanolysis reaction of [MoCl 4 (CH 3 CN) 2 ]. It was shown that the dissolution of 1 in thf results in the formation of the [Mo 2 O 2 Cl 4 (OCH 3 ) 2 (thf) 2 ] (2) and [Mo 2 Cl 4 (OCH 3 ) 4 (thf) 2 ] (3) dimers. A novel tetranuclear 10e molybdenum cluster [Mo 4 Cl 4 O 2 (OCH 3 ) 6 (CH 3 OH) 4 ] (4) was synthesized by the spontaneous disproportionation of 1 in methanol. An alternative pathway to 4 based on the redox reaction of Mo 3+ and [a] Institute

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A Family of Titanium Complexes with Catechol Ligands: Structural Investigation and Catalytic Application

et al. 2016

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Four new titanium catecholate complexes – [Ti2(Cat)2(CatH)2(OCH3)2(CH3OH)2] (1; Cat = C6H4O22–), [Ti2(4tBuCat)4(CH3OH)2]·2CH3OH (2·2CH3OH; 4tBuCat = [4‐t‐C4H9‐C6H3O2]2–), [Ti(Cat)2(dmf)2] (3; dmf = N,N‐dimethylformamide), and [Na(dme)Ti(Cat)3]2[Na(dme)CH3OH]2 (4; dme = 1,2‐dimethoxyethane) – have been obtained by treatment of Ti(OCH3)4 with catechols in methanol and structurally characterized. Complex 3 is the first example of a neutral mononuclear titanium catecholate containing more than one catechol molecule per titanium atom. Complexes 1 and 2 are neutral dimers in the solid state, each with a catechol/Ti ratio equal to 2 and featuring one of the catechol ligands bridging two titanium centres in a singly bridging chelate µ2‐(O,O′,O′) mode. The other catechol molecule is either a terminal bidentate chelating ligand (complex 2) or a Ti monodentate ligand (complex 1). Complex 4 is a heterometallic aryloxide complex with a tetrameric [{Na(dme)Ti(Cat)3)2]2– (Ti2Na2) core as an anionic moiety and Na ions, solvated by methanol and dme ligands – [{Na(dme)(CH3OH)}2]2+ – as a cationic counterpart. Each Ti centre in 4 is octahedrally coordinated by three catechol ligands, demonstrating three distinct types of bridging modality. It was shown that 1–4 effectively catalyze the selective homogeneous hydrogenation of acetylene to ethylene. Various kinetic relationships were determined and analyzed, enabling a reaction pathway for this catalytic reaction to be proposed.

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Methanolysis of MoCl5 in the presence of different alkaline agents; molecular structures of the polynuclear molybdenum(V) methoxides and electron charge density distribution from X-ray diffraction study of the new K–Mo cluster

Cited by 10 publications

References 56 publications

Isolation of a Homoleptic Non-oxo Mo(V) Alkoxide Complex: Synthesis, Structure, and Electronic Properties of Penta-tert-Butoxymolybdenum

Isolation of a Homoleptic Non-oxo Mo(V) Alkoxide Complex: Synthesis, Structure, and Electronic Properties of Penta-tert-Butoxymolybdenum

Developing Pathways to the Synthesis of Low‐Valence Molybdenum Methoxides: Preparation, Characterization, and Redox Chemistry of Dimeric and Tetrameric Molybdenum Alkoxide Clusters

A Family of Titanium Complexes with Catechol Ligands: Structural Investigation and Catalytic Application

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