Synthesis, Structure and Catalytic Properties of Dinuclear Mo<sup>VI</sup> Complexes with Ditopic Diaminotetraphenols

Riisiö, Antti; Lehtonen, Ari; Hänninen, Mikko M.; Sillanpää, Reijo

doi:10.1002/ejic.201201234

Cited by 12 publications

(15 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…156.25 (7) 108.31 (9) 73.51 (6) 95.12 (9) 98.49 (8) 155.90 (19) 106.7 (2) 72.68 (17) 95.3(2) 98.6 (2) 155.73 (16) 107.6(2) 72.98 (14) 95.2 (2) 98.76 (19) Figure 3. Schematic depiction of catalytic epoxidation of substrates S1-5, using complexes 1 and 2 as catalysts.…”

Section: Crystal and Molecular Structures Of H 2 L And [Mo 2 (L)] (M=mentioning

confidence: 99%

“…For example, to obtain robust high-valent metal complexes that are stable under catalytic conditions, a number of bulky anionic ligands with hard oxygen donor atoms have been used. Various phenolate ligands, in particular, have shown great promise towards this end [1][2][3][4][5][6][7][8][9][10]. Amino bisphenols with different side-arm donors are potentially tetradentate ligands that can form stable complexes with all transition metals [11].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Dioxidomolybdenum(VI) and -tungsten(VI) complexes with tripodal amino bisphenolate ligands as epoxidation and oxo-transfer catalysts

et al. 2017

Self Cite

View full text Add to dashboard Cite

The molybdenum(VI) and tungsten(VI) complexes [MO 2 (L)] (M= Mo (1), W (2), H 2 L = bis(2-hydroxy-3,5-di-tert-butybenzyl)morpholinylethylamine)) were synthesized and the complexes were used to catalyse oxotransfer reactions, viz. sulfoxidation, epoxidation and benzoin oxidation. For comparison, the same reactions were catalysed using the known complexes [MO 2 (L')] (M= Mo (3), W (4), H 2 L' = bis(2-hydroxy-3,5-di-tertbutybenzyl)ethanolamine) and [MO 2 (L'')] (M= Mo (5), W (6), H 2 L'' = bis(2-hydroxy-3,5-ditert-butybenzyl)diethyleneglycolamine). The oxo atom transfer activity between DMSO and benzoin at 120 °C was identical for all studied catalysts. Reasonable catalytic activity was observed for sulfoxidation by the molybdenum complexes, but all tungsten complexes were found to be inactive. Similarly, the molybdenum complex 1 exhibited relatively good epoxidation activity, while the corresponding tungsten complex 2 catalysed only the epoxidation of cis-cyclooctene with low activity.

show abstract

Section: Crystal and Molecular Structures Of H 2 L And [Mo 2 (L)] (M=mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dioxidomolybdenum(VI) and -tungsten(VI) complexes with tripodal amino bisphenolate ligands as epoxidation and oxo-transfer catalysts

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…In A and B, the tridentate doubly deprotonated 2,4-di-tertbutyl-6-{[(1-oxido-1-phenylpropan-2-yl) ( aminophenolates (Lehtonen & Sillanpä ä , 2005;Riisiö et al, 2013) and aminoalcoholates (Cross et al, 1999). The Flack (1983) parameter of 0.00 (3) indicates that the crystals of (I) are enantiomerically pure and the absolute configuration has been determined correctly.…”

Section: Commentmentioning

confidence: 99%

A cocrystal of two Mo^VIcomplexes bearing different diastereomers of the 2,4-di-tert-butyl-6-{[(1-oxido-1-phenylpropan-2-yl)(methyl)amino]methyl}phenolate ligand derived from (+)-ephedrine

Sillanpää

Hänninen

2013

Acta Crystallogr C

Self Cite

View full text Add to dashboard Cite

CommentFor the past several decades, high-valent molybdenum complexes have gained considerable attention in various catalytic oxidation reactions (Arzoumanian, 1998) and as biological model compounds (Hille, 1996;Collison et al., 1996). Recently, oxomolybdenum complexes have appeared in novel studies concerning, for example, X-H (X = Si, B, P or H) bond activation (Sousa et al., 2012) and hydrogen production from water (Karunadasa et al., 2010), previously dominated by more noble metals. Ephedrine and its N-substituted derivatives are inexpensive, readily available in enantiomerically pure forms and relatively easy to modify, and thus are an interesting group of chiral ligands for various purposes (Yuan et al., 2003;Kuznetsov et al., 1999;Bouquillon et al., 1999). These two strands of interest are combined in the title compound, (I).The asymmetric unit of (I) contains two distinct Mo VI complexes, A and B, which are conformational diastereomers ( Fig. 1 and Table 1). The bonding and geometric parameters around the Mo VI cation of A and B are comparable to some extent, but several differences can be noted, so the different ligand geometries of the two diastereomers will be discussed.In A and B, the tridentate doubly deprotonated 2,4-di-tert- Figure 1 The molecular structure of complexes A (top) and B (bottom), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and C-bound H atoms have been omitted for clarity.tion geometry for the Mo VI cation. The oxide ligands are strongly bound, with Mo O distances of about 1.7 Å , thus indicating clear double-bond character. The phenoxide and alkoxide O atoms are arranged trans to each other, with a marginally longer Mo-O(phenoxide) distance compared with Mo-O(alkoxide), as might be expected from the different electronic nature and steric hindrance of the groups. The amine N and methanol O atoms are trans to the Mo O groups and rather weakly bound to the Mo VI cation, with relatively long bond lengths of over 2.35 Å . This weaker bonding can be explained by the lack of negative partial charge on the coordinating atoms (amine N and methanol O) and by the considerable trans influence induced by the oxide ligands. The different character of the coordinating groups emphasizes the distortion of the Mo VI octahedron, which is evident from the trans angles around the metal cation (O1-Mo1-N8, O2-Mo1-O5 and O3-Mo1-O4 for A, and O6-Mo2-N38, O7-Mo2-O10 and O8-Mo2-O9 for B; (Cross et al., 1999). The Flack (1983) parameter of 0.00 (3) indicates that the crystals of (I) are enantiomerically pure and the absolute configuration has been determined correctly.The ligand geometries of complexes A and B are notably different, which can be seen from an overlay of the molecules (Fig. 2). The two carbon stereocentres of the L1 2À ligand have the same configuration (1S,2R) in both molecules, but the amine N atoms have different stereochemistries due to the conformational change of the ligand, producing R (N8) and S (N38) configurations for A and B, re...

show abstract

“…The catalytic activity and selectivity rely on the reagents used and the conditions provided [16]. It is necessary to attain the maximum rate of conversion along with the increased yield and to minimize the waste products generated during chemical synthesis [17]. The parameters that have strong influence for the selective catalytic conversions include the type of oxidant, amount of the catalyst and temperature of reaction [18].…”

Section: Introductionmentioning

confidence: 99%

Molybdenum(VI) complexes with tridentate Schiff base ligands derived from isoniazid as catalysts for the oxidation of sulfides: synthesis, X-ray crystal structure determination and spectral characterization

Kargar¹

2021

J IRAN CHEM SOC

View full text Add to dashboard Cite

Two new complexes, including [MoO 2 (L 1 )(CH 3 OH)] and [MoO 2 (L 2 )(CH 3 OH)], with tridentate ONO-donor Schiff base ligands (H 2 L 1 : (E)-N'-(2-hydroxy-3-methoxybenzylidene)isonicotinohydrazide and H 2 L 2 : (E)-N'-(5-chloro-2-hydroxybenzylidene)isonicotinohydrazide) have been synthesized and characterized spectroscopically through FT-IR and 1 H-NMR and by elemental analyses. Their solid-state structures were also confirmed by single-crystal X-ray diffraction (SC-XRD) technique. These tridentate Schiff base ligands coordinated to the metal ion via phenolate oxygen, imine nitrogen and enolic oxygen atoms. In the complexes, the molybdenum center adapts a slightly distorted octahedral geometry, by using three O,N,O-donor atoms of the tridentate ligands, methanol and an oxo group employing the axial positions, while another oxo group makes the equatorial plane. Moreover, the complexes were utilized in oxidizing the different sulfides as an efficient homogeneous catalyst in the presence of tert-butyl hydroperoxide (TBHP) as an oxidizing agent in 1,2-dichloroethane (DCE) as a solvent under refluxed conditions. This method has numerous ascendancies such as high yield, short reaction time and excellent selectivity to produce corresponding sulfoxides without overoxidation to sulfones.

show abstract

Synthesis, Structure and Catalytic Properties of Dinuclear Mo^VI Complexes with Ditopic Diaminotetraphenols

Cited by 12 publications

References 36 publications

Dioxidomolybdenum(VI) and -tungsten(VI) complexes with tripodal amino bisphenolate ligands as epoxidation and oxo-transfer catalysts

Dioxidomolybdenum(VI) and -tungsten(VI) complexes with tripodal amino bisphenolate ligands as epoxidation and oxo-transfer catalysts

A cocrystal of two Mo^VIcomplexes bearing different diastereomers of the 2,4-di-tert-butyl-6-{[(1-oxido-1-phenylpropan-2-yl)(methyl)amino]methyl}phenolate ligand derived from (+)-ephedrine

Molybdenum(VI) complexes with tridentate Schiff base ligands derived from isoniazid as catalysts for the oxidation of sulfides: synthesis, X-ray crystal structure determination and spectral characterization

Contact Info

Product

Resources

About

Synthesis, Structure and Catalytic Properties of Dinuclear MoVI Complexes with Ditopic Diaminotetraphenols

Cited by 12 publications

References 36 publications

Dioxidomolybdenum(VI) and -tungsten(VI) complexes with tripodal amino bisphenolate ligands as epoxidation and oxo-transfer catalysts

Dioxidomolybdenum(VI) and -tungsten(VI) complexes with tripodal amino bisphenolate ligands as epoxidation and oxo-transfer catalysts

A cocrystal of two MoVIcomplexes bearing different diastereomers of the 2,4-di-tert-butyl-6-{[(1-oxido-1-phenylpropan-2-yl)(methyl)amino]methyl}phenolate ligand derived from (+)-ephedrine

Molybdenum(VI) complexes with tridentate Schiff base ligands derived from isoniazid as catalysts for the oxidation of sulfides: synthesis, X-ray crystal structure determination and spectral characterization

Contact Info

Product

Resources

About

Synthesis, Structure and Catalytic Properties of Dinuclear Mo^VI Complexes with Ditopic Diaminotetraphenols

A cocrystal of two Mo^VIcomplexes bearing different diastereomers of the 2,4-di-tert-butyl-6-{[(1-oxido-1-phenylpropan-2-yl)(methyl)amino]methyl}phenolate ligand derived from (+)-ephedrine