Effects of phenanthroline type ligands on the dynamic processes of (.eta.3-allyl)palladium complexes. Molecular structure of (2,9-dimethyl-1,10-phenanthroline)[(1,2,3-.eta.)-3-methyl-2-butenyl]chloropalladium

Hansson, Susanne; Norrby, Per‐Ola; Soegren, Magnus P. T.; Aakermark, Bjoern; Cucciolito, Maria Elena; Giordano, Federico; Vitagliano, Aldo

doi:10.1021/om00036a038

Cited by 121 publications

(73 citation statements)

References 2 publications

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“…As for any coordinating anion, it will accelerate equilibration of the h 3 -allyl intermediate, though not as strongly as, for example, a chloride anion. [21] The results from allylic alkylation of the acetates 2 a-c are listed in Table 1 …”

Section: Resultsmentioning

confidence: 99%

Deconvoluting the Memory Effect in Pd‐Catalyzed Allylic Alkylation: Effect of Leaving Group and Added Chloride

Fristrup

Jensen

Hoppe

et al. 2006

Chemistry A European J

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An analysis of product distributions in the Tsuji-Trost reaction indicates that several instances of reported "memory effects" can be attributed to slow interconversion of the initially formed syn- and anti-[Pd(eta3-allyl)] complexes. Addition of chloride triggers a true memory effect, in which the allylic terminus originally bearing the leaving group has a higher reactivity. The latter effect, termed regioretention, can be rationalized by ionization from a palladium complex bearing a chloride ion, forming an unsymmetrically substituted [Pd(eta3-allyl)] complex. DFT calculations verify that the position trans to the phosphine ligand is more reactive both in the initial ionization and in the subsequent nucleophilic attack.

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Section: Resultsmentioning

confidence: 99%

Deconvoluting the Memory Effect in Pd‐Catalyzed Allylic Alkylation: Effect of Leaving Group and Added Chloride

Fristrup

Jensen

Hoppe

et al. 2006

Chemistry A European J

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“…Coordination of a bidentate ligand in such an asymmetric fashion has been reported very recently for the BIAN ligand 30 and has been observed also for other rigid nitrogen ligands. 62,63 Species IV may be considered to be a T-shaped intermediate in which the fourth coordination site is occupied by a weakly coordinating solvent molecule. A cis-trans isomerization, which is known to proceed rather quickly in this kind of T-shaped intermediate, 54 followed by an alkene association leads to species VI.…”

Section: Discussionmentioning

confidence: 99%

Kinetic Study of the Insertion of Norbornadiene into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(arylimino)acenaphthene

et al. 1997

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Kinetic study of the insertion of norbornadiene into palladium-carbon bonds of complexes containing the rigid bidentate nitrogen ligand Bis(arylimino)acenaphtene Groen, J.H.; Delis, J.G.P.; van Leeuwen, P.W.N.M.; Vrieze, K. Published in: Organometallics DOI:10.1021/om960789fLink to publication Citation for published version (APA):Groen, J. H., Delis, J. G. P., van Leeuwen, P. W. N. M., & Vrieze, K. (1997). Kinetic study of the insertion of norbornadiene into palladium-carbon bonds of complexes containing the rigid bidentate nitrogen ligand Bis(arylimino)acenaphtene. Organometallics, 16, 68-77. DOI: 10.1021/om960789f General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. complexes (1b-12b), bearing the bidentate nitrogen ligand bis(arylimino)acenaphthene (Ar-BIAN), have been synthesized via reaction of the corresponding neutral acylpalladium complexes Pd(C(O)R)X(Ar-BIAN) (1a-12a) with norbornadiene (nbd). For the first time, an extensive kinetic study of this migratory alkene insertion into acyl-palladium bonds of neutral complexes containing R-diimine ligands has been carried out. It has been found that under pseudo-first-order circumstances these reactions follow the rate law k obsd ) k 1 + k 2 [nbd], which shows that these reactions proceed via a pathway independent of alkene concentration (k 1 pathway) and a pathway dependent on alkene concentration (k 2 pathway). The dramatic decrease of the rate constants k 1 and k 2 upon increasing the steric bulk of the BIAN ligand and the large negative entropy of activation and low enthalpy of activation for both pathways indicate that the k 1 and k 2 pathways are closely related and involve associative processes. From the influence of solvent, X and C(O)R ligand, steric and electronic properties of the BIAN ligand, the presence of free halide and free BIAN, and the parameters of activation, mechanisms have been proposed for both pathways. The k 1 pathway may proceed via a rate-determining solvent-assisted halide or nitrogen dissociation, followed by alkene association and migratory insertion, while the k 2 pathway may occur via a rate-determining migratory alkene insertion in a contact ion pair intermediate. This species may be formed via alkene association followed by either halide or nitrogen dissociation.

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“…When the question whether P-N or N-P bonded isomers are formed, if one end of the allyl group co~,tains a CMe2 moiety, is considered, the answer lies in the observation that the CMe2 group is sterically much more hindered by the N-CH(Me) (Ph) function than by the two flat phenyl groups of the PPh2 moiety [40]. So, for complexes lla and 14a the steric influence dominates the electronic factor while the reverse is the case for 13a.…”

Section: Discussionmentioning

confidence: 99%

Methyl-, acetyl- and allyl-palladium and -piatinum complexes containing the novel chiral phosphorus-imine 2-(diphenylphosphino)-benzylidene-S( − )-α-methyl-benzylamine ligand

Ankersmit

Löken

Kooijman

et al. 1996

Inorganica Chimica Acta

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Methyl-, Acetyl-and Allyl-palladium and -Platinum Complexes Containing the Novel Chiral Phorphorous-Imine 2-(diphenyl-phosphino)benzylidene-S(--)-a-methylbenzylamine LigandAnkersmit, H.A.; Loken, B.H.; Kooijman, H.; Spek, A.L.; Vrieze, K.; van Koten, G. Published in:Inorganica Chimica Acta DOI:10.1016/S0020-1693(96)05307-8 Link to publication Citation for published version (APA):Ankersmit, H. A., Loken, B. H., Kooijman, H., Spek, A. L., Vrieze, K., & van Koten, G. (1996). Methyl-, Acetyland Allyl-palladium and -Platinum Complexes Containing the Novel Chiral Phorphorous-Imine 2-(diphenylphosphino)benzylidene-S(--)-a-methyl-benzylamine Ligand. Inorganica Chimica Acta, 252, 141-155. DOI: 10.1016/S0020-1693(96)05307-8 General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. (4a) shows an analogous geometry with a chelating PN ligand, a chloride atom and a methyl group, which is positioned cis to the phosphorus atom, completes the square planar surrounding. The methylpalladium and -platinum complexes reacted with CO to give the corresponding acetyl complexes. The insertion rates increased in the order C!

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Effects of phenanthroline type ligands on the dynamic processes of (.eta.3-allyl)palladium complexes. Molecular structure of (2,9-dimethyl-1,10-phenanthroline)[(1,2,3-.eta.)-3-methyl-2-butenyl]chloropalladium

Cited by 121 publications

References 2 publications

Deconvoluting the Memory Effect in Pd‐Catalyzed Allylic Alkylation: Effect of Leaving Group and Added Chloride

Deconvoluting the Memory Effect in Pd‐Catalyzed Allylic Alkylation: Effect of Leaving Group and Added Chloride

Kinetic Study of the Insertion of Norbornadiene into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(arylimino)acenaphthene

Methyl-, acetyl- and allyl-palladium and -piatinum complexes containing the novel chiral phosphorus-imine 2-(diphenylphosphino)-benzylidene-S( − )-α-methyl-benzylamine ligand

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