Alkene insertion reactions of nitrogen-coordinated acylpalladium(II) complexes. The crystal structure of the dicyclopentadiene insertion product [Pd(C10H12COMe)(bpy)]SO3CF3

Markies, Bertus A.; Rietveld, M.H.P.; Boersma, J.; Spek, Anthony L.; Koten, Gerard van

doi:10.1016/0022-328x(92)80014-o

Cited by 42 publications

(30 citation statements)

References 13 publications

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“…Preliminary attempts to insert a subsequent CO and imine in 6a − c , the putative next step in the copolymerization process, have not been successful, implying a greater degree of stabilization of metallacycles 6a − c than those generated in CO and olefin copolymerizations. Nevertheless, similar phenomena have been noted with certain olefin/CO insertion intermediates and found to be affected by the nature of the olefin and ancillary ligands …”

supporting

confidence: 73%

The Novel Insertion of Imines into a Late-Metal−Carbon σ-Bond: Developing a Palladium-Mediated Route to Polypeptides

1998

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The palladium complex (bipy)Pd(CH 3 )NCC-H 3 + OTf -(2; bipy ) 2,2′-bipyridyl, OTf ) OSO 2 CF 3 ) has been found to undergo the novel sequential insertion of carbon monoxide and imine into the metal-carbon bond in a manner directly analogous to that observed in olefin/CO alternating copolymerizations. The structure of the insertion products, (bipy)Pd[C(Tol)HNRCOC-H 3 ] + OTf -, suggests that the unique combination of CO insertion, amide bond formation, carbonyl oxygen chelation, and resonance stabilization of the chelate ring provides the stabilization required for imine insertion to occur. a Measured by 1 H NMR at 30°C for 3a-d + CD3CN T 2 + 1a-d. b From plot of Keq vs 1/T from 25 to 75°C.

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supporting

confidence: 73%

The Novel Insertion of Imines into a Late-Metal−Carbon σ-Bond: Developing a Palladium-Mediated Route to Polypeptides

1998

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“…The Pd−N(1) bond distance of 2.177(4) Å is longer than the Pd−N(2) distance of 2.053(4) Å, showing that C(13) has a larger trans influence than N(3) of the imine group. The Pd−C(13) bond distance of 2.024(4) Å is comparable to other Pd−C(sp 3 ) bond distances trans to a Pd−N(sp 2 ) bond. ,− The bite angle N(1)−Pd−N(2) is 79.80(15)°, which is normal for (N⌒N)Pd(II) complexes containing bpy or phen ligands. ,,, …”

Section: Resultsmentioning

confidence: 67%

Insertion of Unsaturated Hydrocarbons into the Palladium−Carbon Bond of Complexes (N⌒N)Pd(C(N-2,6-Me₂Ph)Me)X (N⌒N = bpy, phen; X = Cl, Br, I, BF₄): A Structural and Mechanistic Study

Delis¹,

Aubel²,

Vrieze³

et al. 1997

Organometallics

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The reactivity of Pd−carboimine complexes toward unsaturated hydrocarbon bonds has been studied. Insertion of norbornadiene and norbornene into the Pd−C bond of the neutral complexes (N⌒N)Pd(C(N-2,6-Me2C6H3)Me)X (X = Cl (1), Br (2), I (3); N⌒N = 2,2‘-bipyridine (bpy, a), 1,10-phenanthroline (phen, b)) afforded quantitatively the novel and stable complexes [(N⌒N)Pd(C7H8C(NR)Me)]X and [(N⌒N)Pd(C7H10C(NR)Me)]X (R = 2,6-Me2C6H3). Insertion reactions of the unstrained unsaturated hydrocarbons ethylene, propylene, 3-methyl-1,2-butadiene, and acetylene with the cationic complexes [(N⌒N)Pd(C(NR)Me)]X (N⌒N = bpy, phen; R = 2,6-Me2C6H3; X = BF4) provided the complexes [(N⌒N)Pd(C2H4C(NR)Me)]X, [(N⌒N)Pd(C3H6C(NR)Me)]X, [(N⌒N)Pd(C5H8C(NR)Me)]X, and [(bpy)Pd(C2H2C(NR)Me)]X. The remarkable stability of these products is caused by the strong coordination of the carboimine nitrogen to the palladium center. Reaction of 1a and 1b with HC⋮CCOOMe gave, instead of an insertion product, the Michael addition product (N⌒N)Pd[C(CH2)N(2,6-Me2C6H3)(CHCHCOOMe)]Cl. Kinetic measurements carried out on the norbornadiene insertion reactions with 1a,b, 2a, and 3a revealed that the reactions are first order in the palladium concentration and occur via a norbornadiene concentration-independent and dependent pathway.

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“…Palladium compounds are widely utilized for these reactions with ethylene, norbornenes, the other alkenyl compounds, alkenyl halides, aryl alkenyl and alkenyl esters 164–179. The other metal compounds are iron,180–182 manganese183, 184 and rhodium metal compounds 185…”

Section: Synthesis Of Carbonyl Group‐containing Organometallic Intrammentioning

confidence: 99%

Carbonyl group‐containing organometallic intramolecular‐coordination five‐membered ring compounds

Omae¹

2010

Applied Organom Chemis

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Carbonyl group-containing organometallic intramolecular-coordination five-membered ring compounds are easily synthesized by the following five reaction methods: (1) cyclometalation, especially, orthometalation reactions; (2) the reactions of the moieties of an unsaturated carbon-carbon bond attached to a carbonyl group (C C-CO, C C-CO); (3) the reactions of an unsaturated carbon-carbon bond with carbon monoxide (C C and CO, C C and CO); (4) carbonylative ring expansion reactions; and (5) others. These compounds are very easily and regio-specifically synthesized with many kinds of metal compounds, including both transition metals and main group metals. Many of such the reactions are easily applied to organic syntheses.

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Alkene insertion reactions of nitrogen-coordinated acylpalladium(II) complexes. The crystal structure of the dicyclopentadiene insertion product [Pd(C10H12COMe)(bpy)]SO3CF3

Cited by 42 publications

References 13 publications

The Novel Insertion of Imines into a Late-Metal−Carbon σ-Bond: Developing a Palladium-Mediated Route to Polypeptides

The Novel Insertion of Imines into a Late-Metal−Carbon σ-Bond: Developing a Palladium-Mediated Route to Polypeptides

Insertion of Unsaturated Hydrocarbons into the Palladium−Carbon Bond of Complexes (N⌒N)Pd(C(N-2,6-Me₂Ph)Me)X (N⌒N = bpy, phen; X = Cl, Br, I, BF₄): A Structural and Mechanistic Study

Carbonyl group‐containing organometallic intramolecular‐coordination five‐membered ring compounds

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Alkene insertion reactions of nitrogen-coordinated acylpalladium(II) complexes. The crystal structure of the dicyclopentadiene insertion product [Pd(C10H12COMe)(bpy)]SO3CF3

Cited by 42 publications

References 13 publications

The Novel Insertion of Imines into a Late-Metal−Carbon σ-Bond: Developing a Palladium-Mediated Route to Polypeptides

The Novel Insertion of Imines into a Late-Metal−Carbon σ-Bond: Developing a Palladium-Mediated Route to Polypeptides

Insertion of Unsaturated Hydrocarbons into the Palladium−Carbon Bond of Complexes (N⌒N)Pd(C(N-2,6-Me2Ph)Me)X (N⌒N = bpy, phen; X = Cl, Br, I, BF4): A Structural and Mechanistic Study

Carbonyl group‐containing organometallic intramolecular‐coordination five‐membered ring compounds

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Product

Resources

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Insertion of Unsaturated Hydrocarbons into the Palladium−Carbon Bond of Complexes (N⌒N)Pd(C(N-2,6-Me₂Ph)Me)X (N⌒N = bpy, phen; X = Cl, Br, I, BF₄): A Structural and Mechanistic Study