Synthesis, structure, and magnetic properties of new pyridonate–pivalate nickel(II) complex, [Ni11(OH)2(mhp)8(Piv)10(HCO2)2(H2O)2(Hmhp)2(HPiv)2] (mhp = 6-methyl-2-pyridonate), containing formate bridges

Никифорова, М. Е.; Кискин, М. А.; Bogomyakov, A. S.; Александров, Г. Г.; Сидоров, А. А.; Mironov, V. S.; Еременко, И. Л.

doi:10.1016/j.inoche.2010.11.033

Cited by 9 publications

(2 citation statements)

References 18 publications

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“…Dimeric complex 1 is C 2 -symmetric, with each V being seven-coordinate and having distorted pentagonal-bipyramidal geometry. All six pyridonates are κ 2 -bound, with the two central ligands also bridging through the O to the adjacent V center (μ 2 -O), exhibiting a κ 2 :κ 1 bridging mode. − The μ 2 -O interaction is unsymmetrical [V2–O3, 2.184(3) Å; V1–O3, 2.078(3) Å]. The oxidation state of V in 1 can be definitively assigned as V III , as verified using Evan’s method, − where paramagnetic 1 gives μ eff = 2.89 μ B (C 6 D 6 solution, 25 °C), consistent with two unpaired d electrons (μ spin‑only = 2.83 μ B ).…”

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confidence: 94%

Vanadium Pyridonate Catalysts: Isolation of Intermediates in the Reductive Coupling of Alcohols

Griffin

Schafer

2020

Inorg. Chem.

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The reductive coupling of alcohols using vanadium pyridonate catalysts is reported. This attractive approach for C(sp 3 )−C(sp 3 ) bond formation uses an oxophilic, earth-abundant metal for a catalytic deoxygenation reaction. Several pyridonate complexes of vanadium were synthesized, giving insight into the coordination chemistry of this understudied class of compounds. Isolated intermediates provide experimental mechanistic evidence that complements reported computational mechanistic proposals for the reductive coupling of alcohols. In contrast to previous mononuclear vanadium(V)/vanadium(III)/vanadium(IV) cycles, this pyridonate catalyst system is proposed to proceed by a vanadium(III)/vanadium(IV) cycle involving bimetallic intermediates.

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mentioning

confidence: 94%

Vanadium Pyridonate Catalysts: Isolation of Intermediates in the Reductive Coupling of Alcohols

Griffin

Schafer

2020

Inorg. Chem.

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“…While the number of high-nuclearity, non-organometallic complexes of nickel(II) with O-and/or Nbased ligands and without metal-metal bonding continues to grow rapidly [11,15,[29][30][31][32][33] (the record nuclearity is 26 [29]), some nuclearities remain rare. Undecanuclear nickel(II) complexes are particularly rare, and complex 1 thus becomes a new member of the small family of Ni11 clusters [34][35][36][37][38]; the metal topology and core of 1 are novel. (Figure 4).…”

Section: Description Of Structurementioning

confidence: 99%

A Ni11 Coordination Cluster from the Use of the Di-2-Pyridyl Ketone/Acetate Ligand Combination: Synthetic, Structural and Magnetic Studies

et al. 2016

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Abstract:The combined use of di-2-pyridyl ketone, (py) 2 CO, and acetates (MeCO 2´) in nickel(II) chemistry in H 2 O-MeCN under basic conditions (Et 3 N) afforded the coordination cluster [Ni 11 (OH) 6 (O 2 CMe) 12 {(py) 2 C(OH)(O)} 4 (H 2 O) 2 ] (1) in 80% yield, where (py) 2 C(OH)(O)´is the monoanion of the gem-diol form of (py) 2 CO. The complex contains a novel core topology. The core of 1 comprises a central non-linear {Ni 3 (µ 2 -OH) 4 } 2+ subunit which is connected to two cubane {Ni 4 (OH)(µ 3 -OR) 2 (µ 3 -OR 1 )} 4+ subunits [RO´= (py) 2 C(OH)(O)´and R 1 O´= MeCO 2´] via the OHǵ roups of the former which become µ 3 . The linkage of the Ni 3 subunit to each Ni 4 subunit is completed by two η 1 :η 1 :µ 2 and one η 1 :η 3 :µ 4 MeCO 2´g roups. Peripheral ligation is provided by two terminal monodentate MeCO 2´a nd two terminal aqua ligands. The (py) 2 C(OH)(O)´ligands adopt the η 1 :η 1 :η 3 :µ 3 coordination mode. From the twelve MeCO 2´l igands, two are η 1 , two η 1 :η 3 :µ 4 and eight adopt the syn, syn η 1 :η 1 :µ 2 coordination mode; four of the latter bridge Ni II centers at opposite faces of the cubane subunits. Complex 1 is the largest nickel(II)/(py) 2 CO-based ligand coordination cluster discovered to date and has an extremely rare nuclearity (Ni 11 ) in the cluster chemistry of nickel(II). Variable-temperature, solid state dc susceptibility, and variable-field magnetization studies at low temperatures were carried out on complex 1. The study of the data reveals an S = 3 ground state, which has been well rationalized in terms of known magnetostructural correlations and the structural features of 1. An attempt has also been made to interpret the magnetic properties of the undecanuclear cluster in a quantitative manner using four exchange interaction parameters and the obtained J values are discussed. The role of H 2 O in the solvent medium that led to 1, and the high nickel(II) and acetate to di-2-pyridyl ketone reaction ratio employed for its preparation, on the nuclearity and identity of the cluster are critically analyzed.

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An azide-bridged copper(II) 1D-chain with ferromagnetic interactions: synthesis, structure and magnetic studies

et al. 2017

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Synthesis, structure, and magnetic properties of new pyridonate–pivalate nickel(II) complex, [Ni11(OH)2(mhp)8(Piv)10(HCO2)2(H2O)2(Hmhp)2(HPiv)2] (mhp = 6-methyl-2-pyridonate), containing formate bridges

Cited by 9 publications

References 18 publications

Vanadium Pyridonate Catalysts: Isolation of Intermediates in the Reductive Coupling of Alcohols

Vanadium Pyridonate Catalysts: Isolation of Intermediates in the Reductive Coupling of Alcohols

A Ni11 Coordination Cluster from the Use of the Di-2-Pyridyl Ketone/Acetate Ligand Combination: Synthetic, Structural and Magnetic Studies

An azide-bridged copper(II) 1D-chain with ferromagnetic interactions: synthesis, structure and magnetic studies

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