Coordination modes of the novel bifunctional nitrogen ligands 8-(2-pyridyl)quinoline and 8-(6-methyl-2-pyridyl)quinoline towards palladium and platinum. X-ray crystal structures of (8-(2-pyridyl)quinoline)Pd(Me)Cl, (8-(2-pyridyl)quinoline)-Pd(C(O)Me)Cl and (8-(2-pyridyl)quinoline)Pd(PEt3)Cl2

Delis, J.G.P.; Rep, M.; Rülke, Richard E.; Leeuwen, Piet W. N. M. van; Vrieze, K.; Fraanje, Jan; Goubitz, K.

doi:10.1016/s0020-1693(96)05215-2

Cited by 28 publications

(14 citation statements)

References 45 publications

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“…The 1 H NMR data of the complexes 1a , 2a , and 3a at 294 K in CDCl 3 , compiled in Table , show a relatively low-field shift of proton H7 as compared to proton H4. This shift has been observed before for the complexes (8-PQ)M(PEt 3 )Cl 2 (M = Pd, Pt), which is due to the short distance between the proton H7 and the metal center when the ligand is coordinated in a monodentate fashion. − Hence, analogous to the solid structure of 1a , in the nonpolar solvent CDCl 3 the ligand 8-PQ is very likely coordinated in a monodentate fashion. The signals for protons H7 and H4 show a shift to upper and lower field, respectively, upon addition of the polar solvent CD 3 CN to a solution of complexes 1a , 2a , and 3a in CDCl 3 resulting in values for the chemical shifts of these protons comparable to those of complexes 13 and 14 containing a bidentate 8-PQ.…”

Section: Synthetic Resultssupporting

confidence: 55%

“…Both the η 3 -allyl ligand and the chloride are coordinated to palladium. Monodentate coordination of the ligand 8-PQ has been observed before in the complexes (8-PQ)M(PEt 3 )Cl 2 (M = Pd, Pt) . For two other η 3 -allyl complexes (2,9-dimethyl-1,10-phenanthroline)Pd{(1−3-η)-3-methyl-2-butenyl}Cl and ( p -An-BIAN)Pd{(1−3-η)-2-acetyl-3-methyl-2-butenyl}Cl 33 containing very rigid bidentate nitrogen ligands also one nitrogen is dissociated from the palladium and positioned at the apical position above the coordination plane. , …”

Section: Synthetic Resultsmentioning

confidence: 53%

“…Propadiene was purchased from Air Products, while 1,2-heptadiene, ( cis , cis -1,5-cyclooctadiene)Pd(Me)Cl, [Pd(η 3 -C 3 H 5 )Cl] 2 , (8-(2-pyridyl)quinoline)Pd(R)Cl, (bis(p-anisylimino)acenaphthene)Pd(C(O)Me)Cl, (bis( p -anisylimino)acenaphthene)Pd(C(O)Ph)Cl, (2-( N -2-propane-carbaldimino)pyridine)Pd(C(O)Me)Cl, 1,4-di- i -Pr-1,4-diaza-1,3-butadiene, and 1,4-di- p -An-1,4-diaza-1,3-butadiene 40 were synthesized according to previously reported procedures.…”

Section: Methodsmentioning

confidence: 99%

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Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

Delis¹,

Groen²,

Leeuwen³

et al. 1997

Organometallics

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The insertion reactions of the allenes propadiene and 1,2-heptadiene in the Pd-C bond of complexes (NkN)Pd(R)X Cl, Br) have been investigated. An X-ray crystal structure determination of (8-PQ)Pd{(1-3-η)-2-methylpropenyl}Cl exhibited the unexpected monodentate coordination of the nitrogen ligand. The monodentate coordination in apolar solvents and bidentate coordination in polar solvents was demonstrated by means of NOE NMR experiments. Kinetic measurements revealed that the reactions are first order in the palladium concentration and occur via an allene concentration independent and dependent pathway. Reactions of complexes containing flexible bidentate nitrogen ligands were retarded by additional free bidentate nitrogen ligand indicating that initial dissociation of a nitrogen donor is an important step in the reaction. We have strong indications that the migration of the R group to the precoordinated allene is the rate-determining step. Instead of masslaw retardation by excess X -(X ) Cl -, Br -), an enhancement of the reaction has been observed in case of the complexes (8-PQ)Pd(Me)Cl, (8-PQ)Pd(Me)Br, and (i-Pr-DAB)Pd(C(O)-Me)Cl. Flexible bidentate nitrogen ligands greatly enhance the reaction, owing to the easy formation of an accessible site on the metal center. The insertion of allenes into the Pd-C bonds of complexes containing rigid bidentate nitrogen ligands probably proceeds via initial allene association followed by either halide or nitrogen dissociation and subsequent migration of the R group to the precoordinated allene.

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Section: Synthetic Resultssupporting

confidence: 55%

Section: Synthetic Resultsmentioning

confidence: 53%

Section: Methodsmentioning

confidence: 99%

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Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

Delis¹,

Groen²,

Leeuwen³

et al. 1997

Organometallics

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“…Isocyanides might allow the observation of intermediate complexes and variation of electronic and steric factors by variation of the R group on the nitrogen atom, and moreover, it would be of great interest to look at the possibility for the direct synthesis of the polyimine analogue of polyketone. Since it is known that complexes having bidentate nitrogen ligands allow fast insertions of CO and olefins, − ,,, we wished to explore the prospect of copolymerization of isocyanides and olefins. Isocyanide insertion into Pd−C bonds has been extensively studied, − but mainly for complexes containing phosphine ligands. − We describe in this report, of which a preliminary account has already appeared, the insertion of isocyanides into the Pd−Me bond of (N⌒N)Pd(Me)Cl complexes, the characterization of the reaction intermediates, and a detailed kinetic study of the isocyanide association, isocyanide dissociation, and methyl migration reaction.…”

Section: Introductionmentioning

confidence: 99%

Isocyanide Insertion into the Palladium−Carbon Bond of Complexes Containing Bidentate Nitrogen Ligands: A Structural and Mechanistic Study

Delis¹,

Aubel²,

Vrieze³

et al. 1997

Organometallics

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Isocyanide insertion into the palladium-carbon bond of complexes containing bidentate nitrogen ligands; A structural and mechanistic study Delis, J.G.P.; Aubel, P.G.; Vrieze, K.; van Leeuwen, P.W.N.M.; Veldman, N.; Spek, A.L.; van Neer, F.J.R. Published in: Organometallics DOI:10.1021/om970096eLink to publication Citation for published version (APA):Delis, J. G. P., Aubel, P. G., Vrieze, K., van Leeuwen, P. W. N. M., Veldman, N., Spek, A. L., & van Neer, F. J. R. (1997). Isocyanide insertion into the palladium-carbon bond of complexes containing bidentate nitrogen ligands; A structural and mechanistic study. Organometallics, 16, 2948-2957. DOI: 10.1021/om970096e 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. Insertion of the isocyanides 2,6-dimethylphenyl isocyanide (DIC), tert-butyl isocyanide (TIC) and tosylmethyl isocyanide (TosMIC) into the Pd-Me bond of complexes (NkN)Pd(Me)Cl (NkN ) 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 2,2′-bipyrimidine (bpm)) afforded quantitatively (NkN)Pd(C(dNsR)Me)Cl (R ) 2,6-Me 2 C 6 H 3 , t-Bu, CH 2 Tosyl). The course of the reaction has been shown to proceed via the intermediates [(NkN)Pd(CN-R)(Me)]Cl (NkN ) bpy, phen; R ) 2,6-Me 2 C 6 H 3 , t-Bu, CH 2 Tosyl), which have been characterized at 250 K by NMR and IR spectroscopies and conductivity measurements. The mechanism of the insertion reaction involves substitution of the halide by the isocyanide followed by a rate-determining methyl migration to the precoordinated isocyanide. Kinetic measurements of the isocyanide insertion reaction, which provided the reaction rate constants of the isocyanide association (k 1 ), isocyanide dissociation (k -1 ), and methyl migration reaction (k 2 ), have demonstrated that the migration rate of the methyl group to the precoordinated isocyanide increases with increasing electrophilicity of the isocyanide. Methyl migration in the intermediate complexes [(NkN)Pd(CN-R)(Me)]Cl (NkN ) bpy, phen; R ) 2,6-Me 2 C 6 H 3 , t-Bu, CH 2 Tosyl) also occurs in the solid state. The complexes (NkN)Pd(C(dNsR)Me)X (NkN ) bpy, phen; R ) t-Bu, CH 2 Tosyl; X ) Cl, Br) show a fluxional behavior due to a site exchange of the nitrogen donor atoms. Spin saturation transfer 1 H NMR experiments showed that the mechanism of this process involves Pd-N bond breaki...

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“…[Ru(dmb) 2 (8pyq)] 2+ was successfully synthesized via a typical synthetic route shown in Scheme S1. 8pyq was synthesized according to the literature 35 and then introduced into a metal complex. A PF 6 − ion was selected as the counterion of the complex due to high solubility of the PF 6 − salt of polypyridyl ruthenium(II) complex in polar organic solvents.…”

Section: ∫ ∫mentioning

confidence: 99%

Electrochemical and Spectroscopic Behaviors of a Novel Ruthenium(II) Complex with a Six-Membered Chelate Structure

Ito

Matsui

2019

Inorg. Chem.

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A novel polypyridyl ruthenium(II) complex with a sixmembered chelate ring ([Ru(dmb) 2 (8pyq)] 2+ ) was designed and synthesized. The oxidation potential was shifted to the negative potential direction, and relatively intense metal-to-ligand charge transfer absorption in the longerwavelength region was observed for [Ru(dmb) 2 (8pyq)] 2+ compared with the reference complexes without any six-membered chelate rings. The electrochemical and spectroscopic properties of [Ru(dmb) 2 (8pyq)] 2+ were discussed in terms of the chelate structure and coordination geometry with utilization of theoretical calculations.

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Coordination modes of the novel bifunctional nitrogen ligands 8-(2-pyridyl)quinoline and 8-(6-methyl-2-pyridyl)quinoline towards palladium and platinum. X-ray crystal structures of (8-(2-pyridyl)quinoline)Pd(Me)Cl, (8-(2-pyridyl)quinoline)-Pd(C(O)Me)Cl and (8-(2-pyridyl)quinoline)Pd(PEt3)Cl2

Cited by 28 publications

References 45 publications

Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

Isocyanide Insertion into the Palladium−Carbon Bond of Complexes Containing Bidentate Nitrogen Ligands: A Structural and Mechanistic Study

Electrochemical and Spectroscopic Behaviors of a Novel Ruthenium(II) Complex with a Six-Membered Chelate Structure

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