Fluoride Displacement by Lithium Reagents. An Improved Method for the Synthesis of Nickel Hydroxo, Alkoxo, and Amido Complexes

Cámpora, Juan; Matas, Inmaculada; Graiff, Claudia; Tiripicchio, António

doi:10.1021/om0489709

Cited by 41 publications

(32 citation statements)

References 46 publications

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“…[16] The [Ni II (OH)(14-tmc)] + complex showed as quare pyramidal geometry,i na greement with its high-spin S = 1c haracter.M ore commona re diamagnetich ydroxonickel(II) species with the metal center in as quare planar environment typical for d 8 metals, such as diphosphine-based systems including [Ni II (OH)(PNP)] [17] andt he organometallic complexes [Ni II (OH)(PCP)] and [Ni II (OH)(Me)(dippe)] ( Figure 3). [18,19] A distorteds quare planar geometry was observed in [Ni II (OH)(Mebuea)] À . [20] In this case, an etwork of intramolecular hydrogen-bonding interactions was established between the hydroxo ligand and the amide NH groups of the Mebuea ligand.F inally,n os tructural information has been gathered for hydroxonickel(III) species, but EPR and vibrational characterization of such compounds has been achieved in afew cases.…”

Section: Well-defined Nickel-oxygen Species 21 Hydroxonickel and Rementioning

confidence: 98%

“…The [Ni II (OH)(14‐tmc)] + complex showed a square pyramidal geometry, in agreement with its high‐spin S= 1 character. More common are diamagnetic hydroxonickel(II) species with the metal center in a square planar environment typical for d 8 metals, such as diphosphine‐based systems including [Ni II (OH)(PNP)] and the organometallic complexes [Ni II (OH)(PCP)] and [Ni II (OH)(Me)(dippe)] (Figure ) . A distorted square planar geometry was observed in [Ni II (OH)(Mebuea)] − .…”

Section: Well‐defined Nickel–oxygen Speciesmentioning

confidence: 99%

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Spectroscopically Characterized Synthetic Mononuclear Nickel–Oxygen Species

Corona

2016

Chemistry A European J

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Iron, copper, and manganese are the predominant metals found in oxygenases that perform efficient and selective hydrocarbon oxidations and for this reason, a large number of the corresponding metal-oxygen species has been described. However, in recent years nickel has been found in the active site of enzymes involved in oxidation processes, in which nickel-dioxygen species are proposed to play a key role. Owing to this biological relevance and to the existence of different catalytic protocols that involve the use of nickel catalysts in oxidation reactions, there is a growing interest in the detection and characterization of nickel-oxygen species relevant to these processes. In this Minireview the spectroscopically/structurally characterized synthetic superoxo, peroxo, and oxonickel species that have been reported to date are described. From these studies it becomes clear that nickel is a very promising metal in the field of oxidation chemistry with still unexplored possibilities.

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Section: Well-defined Nickel-oxygen Species 21 Hydroxonickel and Rementioning

confidence: 98%

Section: Well‐defined Nickel–oxygen Speciesmentioning

confidence: 99%

Spectroscopically Characterized Synthetic Mononuclear Nickel–Oxygen Species

Corona

2016

Chemistry A European J

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“…Using steric effects in this manner is also effective in synthetic systems, as most synthetic terminal nickel hydroxido and aqua complexes use sterically encumbered ligand frameworks around the metal center to prevent bridging. Cámpora prepared the earliest examples of monomeric square planar terminal Ni II –OH moieties [16,17], and a number of similar 4-coordinate terminal Ni II –OH complexes have been developed for catalysis [18–21]. To the best of our knowledge, there are only two examples of crystallographically characterized monometallic 5-coordinate Ni II –OH complexes.…”

Section: Introductionmentioning

confidence: 99%

Terminal NiII−OH/−OH2 complexes in trigonal bipyramidal geometries derived from H2O

2017

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The preparation and characterization of two NiII complexes are described, a terminal NiII–OH complex with the tripodal ligand tris[(N)-tertbutylureaylato)-N-ethyl)]aminato ([H3buea]3−) and a terminal Ni II–OH2 complex with the tripodal ligand N,N′,N″-[2,2′,2″-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido) ([MST]3−). For both complexes, the source of the –OH and –OH2 ligand is water. The salts K2[NiIIH3buea(OH)] and NMe4[NiIIMST(OH2)] were characterized using perpendicular-mode X-band electronic paramagnetic resonance, Fourier transform infrared, UV-visible spectroscopies, and its electrochemical properties were evaluated using cyclic voltammetry. The solid state structures of these complexes determined by X-ray diffraction methods reveal that they adopt a distorted trigonal bipyramidal geometry, an unusual structure for 5-coordinate NiII complexes. Moreover, the NiII–OH and NiII–OH2 units form intramolecular hydrogen bonding networks with the [H3buea]3− and [MST]3− ligands. The oxidation chemistry of these complexes was explored by treating the high-spin NiII compounds with one-electron oxidants. Species were formed with S = 1/2 spin ground states that are consistent with formation of monomeric NiIII species. While the formation of NiIII–OH complexes cannot be ruled out, the lack of observable O-H vibrations from the putative Ni–OH units suggest the possibility that other high valent Ni species are formed.

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“…Table 5 shows the term energies and equilibrium distances of the optimised structures of selected terms. The relaxation of the structure of the 6 A 2 term leads to an energy lower by [19][20][21][22] The values are longer than the value of 182 pm for the bare Ni 2 (OH) 2 + system. But since these complexes contain more ligands, weaker bond strengths for the individual bonds and therefore larger bond distances should be expected.…”

Section: Ni 2 (Oh)mentioning

confidence: 99%

MRCI investigation of different isomers of Ni₂O₂H₂⁺

Hübner

Himmel

2011

Phys. Chem. Chem. Phys.

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The geometrical and electronic structures of different isomers of Ni(2)O(2)H(2)(+) are investigated by multireference configuration interaction (MRCI) calculations using natural atomic orbital basis sets. The lowest-lying isomer, Ni(2)(OH)(2)(+), has a rhombic shape with two OH groups bridging the Ni atoms. The next isomer in energetic order with a relative energy of 0.29 eV consists of a linear NiONi(OH(2))(+) chain. Other structures with a rhombic shape, (NiH)(2)O(2)(+), with H bound to the Ni atoms have considerably higher energies, above 4 eV. Especially the low-lying isomers are characterised by a large number of low-lying electronic terms. The product Ni(2)O(2)H(2)(+) of the reaction of Ni(2)O(2)(+) with small alkanes is likely to have the rhombic Ni(2)(OH)(2)(+) structure. The reaction energy of the reaction Ni(2)O(2)(+) + H(2)→ Ni(2)(OH)(2)(+) is estimated to be about -3.5 eV.

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Fluoride Displacement by Lithium Reagents. An Improved Method for the Synthesis of Nickel Hydroxo, Alkoxo, and Amido Complexes

Cited by 41 publications

References 46 publications

Spectroscopically Characterized Synthetic Mononuclear Nickel–Oxygen Species

Spectroscopically Characterized Synthetic Mononuclear Nickel–Oxygen Species

Terminal NiII−OH/−OH2 complexes in trigonal bipyramidal geometries derived from H2O

MRCI investigation of different isomers of Ni₂O₂H₂⁺

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Fluoride Displacement by Lithium Reagents. An Improved Method for the Synthesis of Nickel Hydroxo, Alkoxo, and Amido Complexes

Cited by 41 publications

References 46 publications

Spectroscopically Characterized Synthetic Mononuclear Nickel–Oxygen Species

Spectroscopically Characterized Synthetic Mononuclear Nickel–Oxygen Species

Terminal NiII−OH/−OH2 complexes in trigonal bipyramidal geometries derived from H2O

MRCI investigation of different isomers of Ni2O2H2+

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MRCI investigation of different isomers of Ni₂O₂H₂⁺