Steric Control of Coordination Number:  A Series of Mo(VI) Dioxo Diaryloxide Complexes Bearing 4-, 5-, and 6-Coordinate Environments

Hanna, Tracy A.; Ghosh, Amit; Ibarra, Catalina; Méndez‐Rojas, Miguel A.; Rheingold, Arnold L.; Watson, William H.

doi:10.1021/ic035129z

Cited by 29 publications

(23 citation statements)

References 25 publications

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“…The Mo-Osolvent bond trans to the oxido group is considerably longer than the Mo-Ophenolate bond due to the strong trans influence of the oxido group. These features as well as the O=Mo=O angles and the Mo=O bonds are similar to those found for other mononuclear cis-[MoO2] 2+ complexes [9,[30][31][32][33] [33,[37][38][39]. In general, there are rather small differences between the structural parameters around the Mo centre in monomeric 1 compared with the dimeric 2 and 4 (see Table 2).…”

Section: Crystal and Molecular Structuressupporting

confidence: 83%

Catalytic epoxidation using dioxidomolybdenum(VI) complexes with tridentate aminoalcohol phenol ligands

Hossain

Schachner

Haukka

et al. 2019

Inorganica Chimica Acta

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Section: Crystal and Molecular Structuressupporting

confidence: 83%

Catalytic epoxidation using dioxidomolybdenum(VI) complexes with tridentate aminoalcohol phenol ligands

Hossain

Schachner

Haukka

et al. 2019

Inorganica Chimica Acta

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“…The square‐pyramidal arrangement of the ligands in 3 is thus unique. The successful isolation of the known compounds has been ascribed to the employment of bulky ligands and this hypothesis has very recently been confirmed in a systematic study 16…”

Section: Resultsmentioning

confidence: 80%

Metalation of 2‐Propenylphenol

2004

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In order to generate 2‐propenylphenolate, PO−, as a potential ligand for oxomolybdenum compounds, the lithiation of the parent phenol derivative, POH, was investigated. Treatment of POH with BuLi in THF yielded a tetramer of the corresponding alkoxide “POLi” with a heterocubane structure in which the coordination spheres of the Li centres are completed by THF molecules, i.e. {Li(THF)[μ3‐OC6H4(CH=CH−CH3)‐2]}4 (1). Compound 1 proved to be rather unreactive and unsuitable as a starting material for the introduction of the corresponding aryloxide ligands into the coordination sphere of molybdenum by salt metathesis. The latter did occur, however, when “POLi” was synthesised in the presence of 12‐crown‐4 and subsequently treated with molybdenyl chloride. This led to an unidentified aryloxide compound as well as to a hitherto unknown chlorooxomolybdate anion in the complexes [Li(12‐crown‐4)][MoO2Cl3(THF)] (2) and [{Li(12‐crown‐4)}2Cl][MoO2Cl3(THF)] (2′) with an octahedral coordination sphere at the molybdenum centre in each case. An Mo(PO) complex was finally isolated for the first time when MoO2(OtBu)2 was employed as a starting material and treated with “POLi” prepared in situ in the presence of the crown ether. This led to the isolation of [Li(12‐crown‐4)2][MoO2(PO)3] (3), which represents a rare example of a five‐coordinate dioxomolybdenum(VI) complex as well as being the first example among these complexes with a square‐pyramidal ligand arrangement. Comparison of 2 with 3 suggests that the low coordination number of the 14‐electron compound 3 originates from the bulkiness of the PO− ligands. The crystal structures of all three compounds 1−3 are discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…In this compound (MoO 2 L 4 ) the coordination geometry of Mo(VI) is similar to that observed earlier [50], which consist of two oxo oxygen atoms, one enolate oxygen, one phenolate oxygen, and an azomethine nitrogen atom. This is the rare example of a five-coordinate Mo(VI) complex [50,53].…”

Section: Description Of the X-ray Structure Of Complexmentioning

confidence: 98%

Synthesis, structural studies and catalytic activity of dioxidomolybdenum(VI) complexes with aroylhydrazones of naphthol-derivative

et al. 2014

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Reaction of the salicylhydrazone of 2-hydroxy-1-naphthaldehyde (H 2 L 1), anthranylhydrazone of 2hydroxy-1-naphthaldehyde (H 2 L 2), benzoylhydrazone of 2-hydroxy-1-acetonaphthone (H 2 L 3) and anthranylhydrazone of 2-hydroxy-1-acetonaphthone (H 2 L 4 ; general abbreviation H 2 L) with [MoO 2 (acac) 2 ] afforded a series of 5-and 6-coordinate Mo(VI) complexes of the type [MoO 2 L 1-2 (ROH)] [where R = C 2 H 5 (1) and CH 3 (2)], and [MoO 2 L 3-4 ] (3 and 4). The substrate binding capacity of 1 has been demonstrated by the formation of one mononuclear mixed-ligand dioxidomolybdenum complex [MoO 2 L 1 (Q)] {where Q = c-picoline (1a)}. Molecular structure of all the complexes (1, 1a, 2, 3 and 4) is determined by X-ray crystallography, demonstrating the dibasic tridentate behavior of ligands. All the complexes show two irreversible reductive responses within the potential window À0.73 to À1.08 V, due to Mo VI /Mo V and Mo V /Mo IV processes. Catalytic potential of these complexes was tested for the oxidation of benzoin using 30% aqueous H 2 O 2 as an oxidant in methanol. At least four reaction products, benzoic acid, benzaldehydedimethylacetal, methyl benzoate and benzil were obtained with the 95-99% conversion under optimized reaction conditions. Oxidative bromination of salicylaldehyde, a functional mimic of haloperoxidases, in aqueous H 2 O 2 /KBr in the presence of HClO 4 at room temperature has also been carried out successfully.

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Steric Control of Coordination Number: A Series of Mo(VI) Dioxo Diaryloxide Complexes Bearing 4-, 5-, and 6-Coordinate Environments

Cited by 29 publications

References 25 publications

Catalytic epoxidation using dioxidomolybdenum(VI) complexes with tridentate aminoalcohol phenol ligands

Catalytic epoxidation using dioxidomolybdenum(VI) complexes with tridentate aminoalcohol phenol ligands

Metalation of 2‐Propenylphenol

Synthesis, structural studies and catalytic activity of dioxidomolybdenum(VI) complexes with aroylhydrazones of naphthol-derivative

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