2015
DOI: 10.1002/chem.201500652
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β‐Hydrogen Elimination Reactions of Nickel and Palladium Methoxides Stabilised by PCP Pincer Ligands

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Cited by 26 publications
(20 citation statements)
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“…With facile βelimination occurring from Ni alkyl complexes with β hydrogens, we were interested in whether suitably substituted Ni alkoxy, thiolate, or amido complexes would also undergo βelimination. This is known to occur for similar Ni PCP pincer alkoxy complexes 91,92 (ECHRR′), where E = NR′′, O, eliminate methane to generate the corresponding Ni(0) η 2 -imine, aldehyde, and ketone derivatives as shown in eq 3. 81 However, mechanistic studies indicate that simple β-elimination followed by reductive elimination is likely not happening as the transformations appear to be catalyzed by trace impurities.With the related dtbpe ligand (dtbpe = Bu t 2 PC 2 H 4 PBu t 2 ), similar Ni(0) compounds have been synthesized and isolated containing C−O and C−S double bonds (Figure 5), however, not by β-elimination.…”
Section: ■ Results and Discussionmentioning
confidence: 99%
“…With facile βelimination occurring from Ni alkyl complexes with β hydrogens, we were interested in whether suitably substituted Ni alkoxy, thiolate, or amido complexes would also undergo βelimination. This is known to occur for similar Ni PCP pincer alkoxy complexes 91,92 (ECHRR′), where E = NR′′, O, eliminate methane to generate the corresponding Ni(0) η 2 -imine, aldehyde, and ketone derivatives as shown in eq 3. 81 However, mechanistic studies indicate that simple β-elimination followed by reductive elimination is likely not happening as the transformations appear to be catalyzed by trace impurities.With the related dtbpe ligand (dtbpe = Bu t 2 PC 2 H 4 PBu t 2 ), similar Ni(0) compounds have been synthesized and isolated containing C−O and C−S double bonds (Figure 5), however, not by β-elimination.…”
Section: ■ Results and Discussionmentioning
confidence: 99%
“…Therefore, we removed conformational uncertainty by replacing i ‐propyl substituents by methyl groups ( i. e ., Me PCP ligand instead of iPr PCP). In our own experience, [14b,15a] and also for others, [26,28b] this simplification does not have excessive impact on the main conclusions. As shown below, the agreement between experimental and computed data proves satisfactory in general.…”
Section: Resultsmentioning
confidence: 56%
“…As represented in Scheme , the irreversible evolution of 23 a into a nickel(0) carbonyl is brought about by formaldehyde, with loss of H 2 . The identification of 23 a and 23 b enabled us to gather experimental thermodynamic and kinetic data for the β‐elimination step, and compare with the results of DFT calculations . The parameters shown in Scheme confirm that for both M=Ni and Pd, β‐elimination is reversible and slightly endothermic.…”
Section: Introductionmentioning
confidence: 78%