2020
DOI: 10.1021/acs.organomet.0c00615
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Abstract: The cycloneophylpalladium­(II) complexes [Pd­(CH2CMe2C6H4)­(κ2 -N,N′- L)] (L = RO­(CH2)3N­(CH2–2-C5H4N)2, R = H, Me) undergo oxidation to Pd­(IV) with bromine or iodine to give [PdX­(CH2CMe2C6H4)­(κ3 -N,N′,N″- L)]­X (X = Br, I) or with methyl iodide to give the transient complexes [PdMe­(CH2CMe2C6H4)­(κ3 -N,N′,N″- L)]­I. The products of Br2 and I2 oxidation, [PdX­(CH2CMe2C6H4)­(κ3 -N,N′,N″- L)]­X (X = Br, I), are sufficiently stable to be isolated, but they decompose slowly in solution by reductive elimination… Show more

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Cited by 8 publications
(4 citation statements)
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References 66 publications
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“…These catalytic intermediates can form via oxidation of M­(II) and M­(III) complexes ,,, or even via oxidative addition of RX electrophiles to Pd­(II) complexes. Organometallic complexes Pd­(IV) and Ni­(IV) are usually more stable than similar complexes of Pd­(III) and Ni­(III). Many well-defined Pd­(IV) complexes containing chelated ligands coordinated to palladium via Pd–C­(sp 2 ) or Pd–C­(sp 3 ) bonds have been prepared, and reductive elimination of these complexes to give C–C and C–X coupling products was studied in detail. , …”
Section: Main Partmentioning
confidence: 99%
“…These catalytic intermediates can form via oxidation of M­(II) and M­(III) complexes ,,, or even via oxidative addition of RX electrophiles to Pd­(II) complexes. Organometallic complexes Pd­(IV) and Ni­(IV) are usually more stable than similar complexes of Pd­(III) and Ni­(III). Many well-defined Pd­(IV) complexes containing chelated ligands coordinated to palladium via Pd–C­(sp 2 ) or Pd–C­(sp 3 ) bonds have been prepared, and reductive elimination of these complexes to give C–C and C–X coupling products was studied in detail. , …”
Section: Main Partmentioning
confidence: 99%
“…It follows that oxidation and reduction reactions can be promoted by changes in coordination numbers. For example, reduction of six-coordinate octahedral Pd­(IV) or Pt­(IV) complexes occurs more readily after ligand loss affords a five-coordinate intermediate. There are several studies of oxidation/reduction chemistry with complexes containing SRLs that change coordination mode depending on the oxidation state of the metal. Even challenging small molecule reduction (e.g., of N 2 , PhN = NPh or O 2 ) can be achieved by metals (e.g., Mo­(III) or W­(II)), in which the SRL stabilizes a masked low-coordinate structure. , …”
Section: Influence Of Srls On Fundamental Organometallic Reactionsmentioning
confidence: 99%
“…Kinetic and mechanistic investigations of the oxidative addition reactions of organoplatinum(II) complexes have clearly proved that these reactions follow an S N 2 mechanism [ 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 ] with the exception of a few cases [ 46 , 47 ]. The S N 2 mechanism with a large negative ∆S ≠ value can be observed for the small organic molecules, such as alkyl halides [ 48 , 49 , 50 , 51 ].…”
Section: Introductionmentioning
confidence: 99%