The role of solvent in organometallic chemistry — Oxidative addition with dichloromethane or chloroform

Abo-Amer, Anwar; McCreadyMatthew, S; ZhangFenbao,; PuddephattRichard, J

doi:10.1139/v11-096

Cited by 32 publications

(14 citation statements)

References 63 publications

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“…The oxidative addition of chloroform to complex 1 resulting in complex 1a has been reported before, but no crystal structure was described. 45,48 A triangular plane is formed by both sulfur atoms from the tridentate mdeta ligand and the carbon atom from the CHCl 2 − unit. The axial positions of the bipyramid are occupied by the bridging nitrogen and the coordinated chloride.…”

Section: Resultsmentioning

confidence: 99%

Single source precursor route to nanometric tin chalcogenides

et al. 2021

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Section: Resultsmentioning

confidence: 99%

Single source precursor route to nanometric tin chalcogenides

et al. 2021

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“…Attempts to purify Pt-Br by chromatography on basic alumina with CH 2 Cl 2 as the eluent resulted in halide exchange, putatively via oxidative addition of CH 2 Cl 2 and reductive elimination of CH 2 BrCl to form complex Pt-Cl. 98,99 A second possible reaction sequence is the bromide abstraction by alumina resulting in a cationic complex that subsequently reacts with CH 2 Cl 2 to form Pt-Cl. When basic alumina was added to CD 2 Cl 2 solutions of Pt-Br that were kept in the dark, exchange of the bromido by the chlorido ligand was much slower and occurred only over a period of two weeks as probed by 31 P NMR spectroscopy.…”

Section: Synthesismentioning

confidence: 99%

Dual ligand-based fluorescence and phosphorescence emission at room temperature from platinum thioxanthonyl complexes

2015

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New square-planar platinum(II) complexes of the type trans-[Pt(PEt3)2(Tx)(X)] (X = Br, Cl, I or CN) bearing a σ-bonded thioxanthon-2-yl (Tx) ligand have been prepared and characterised by X-ray crystallography, cyclic voltammetry, and by NMR and electronic absorption and luminescence spectroscopy. The ligand X hardly influences the electronic transitions, which indicates that the relevant molecular orbitals are largely confined to the Pt-Tx chromophore. In agreement with TD-DFT calculations the energetically lowest electronic transition is assigned as the Tx-centred π→π* HOMO → LUMO excitation. All four complexes display dual emission from the σ-bonded Tx ligand at ca. 450 nm and at ca. 510 nm, which are assigned as fluorescence originating from the (1)π*-state and as phosphorescence originating from the (3)π*-state, respectively. The phosphorescence quantum yield increases with increasing σ-donor strength of the ligand X and reaches a uniquely high value of 18.8% for the chlorido complex Pt-Cl. Switching-on of Tx phosphorescence emission by the Pt(PEt3)2(X) fragment goes along with a reduction of the lifetime of the Tx triplet state from several ms in purely organic derivatives to ca. 2 μs in the complexes.

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“…The operation of LAG in organometallic systems is particularly complex, as direct solvent involvement in the coordination sphere of a metal can produce a variety of reaction outcomes, whether by generation of weak interactions that are easily replaced with other substrates (so-called “virtual” or “latent” sites) , or by more direct changes, such as oxidative addition. − Despite such issues, the η parameter has found repeated use as a descriptor in organometallic reactions. − …”

Section: Introductionmentioning

confidence: 99%

Solvate-Assisted Grinding: Metal Solvates as Solvent Sources in Mechanochemically Driven Organometallic Reactions

DeGroot

Hanusa

2021

Organometallics

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Solvent effects in synthetic chemistry can be analyzed in various ways, but a possibly counterintuitive approach is to remove the solvent entirely from the reaction environment. Mechanochemical initiation (grinding or milling of solid reagents) can then be used to replace the mixing and energy that would be supplied by a solvent. The effect of complete solvent elimination can be unpredictable, however, and even partial removal, as found in the realm of liquid-assisted grinding (LAG), can alter reaction outcomes profoundly. Reduced quantities of solvents can also be present in the form of solvates, and although their use has been classified under the category of “neat” or “dry” grinding, “solvate-assisted grinding” (SAG) might be a more descriptive term, as the outcome of such reactions can differ from those of both LAG and neat grinding, with the latter term more properly restricted to the use of anhydrous or unsolvated reagents only. This study examines the mechanochemically driven synthesis of the bis(allyl)metal complexes [MA′2] (M = Cr, Fe, Co, Ni; A′ = 1,3-(SiMe3)2C3H3) via halide metathesis. Particular emphasis is given to the nickel-based system, whose synthesis from nickel halide solvates is compared with the same reaction using the anhydrous metal halide and either large or LAG quantities of solvent (a few microliters of solvent per milligram of reagents). The reactions employing solvate-assisted grinding, either alone (e.g., with [Ni(py)4Cl2]) or with LAG amounts of a different solvent (e.g., with [Ni(dme)Br2] and THF as the LAG solvent) yield the nickel allyl complex the most efficiently, suggesting that the intimate interaction of coordinated solvents with the metal centers is an important variable in determining the outcome of the metathesis reactions. Although they were developed in the context of mechanochemically driven reactions, these results have implications for solution-based synthesis as well, where the use of solvated reagents can strongly affect outcomes.

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The role of solvent in organometallic chemistry — Oxidative addition with dichloromethane or chloroform

Cited by 32 publications

References 63 publications

Single source precursor route to nanometric tin chalcogenides

Single source precursor route to nanometric tin chalcogenides

Dual ligand-based fluorescence and phosphorescence emission at room temperature from platinum thioxanthonyl complexes

Solvate-Assisted Grinding: Metal Solvates as Solvent Sources in Mechanochemically Driven Organometallic Reactions

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