Configuration of imino carbon palladated pyridine-2-carbaldimines. Crystal and molecular structure of trans-chlorobis(dimethylphenylphosphine)[(p-methoxyphenyl)imino](2-pyridyl)methyl]palladium(II)

Crociani, B.; Sala, Marcellina.; Polo, A.; Bombieri, G.

doi:10.1021/om00138a012

Cited by 40 publications

(14 citation statements)

References 2 publications

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“…All protons of azomethine and salicylic moieties of these complexes were shifted upfield while the aromatic ring protons exhibited either downfield shift or remained unchanged (in Section 2) compared with those of the free ligands. Similar magnetic shielding effects were previously observed in the Schiff-base complexes of Pd(II), Zn(II), Co(II) and Cu(II) [27][28][29][30]. In the 13 The main stretching frequencies of the IR spectra of ligands (L n ) and their mono-and dinuclear Pd(II) complexes are given in the experimental section.…”

Section: Synthesis and Characterizationsupporting

confidence: 66%

Mono- and dinuclear Pd(II) complexes of different salicylaldimine ligands as catalysts of transfer hydrogenation of nitrobenzene with cyclohexene and Suzuki–Miyaura coupling reactions

Taş

Kılıç

Durgun

et al. 2009

Journal of Organometallic Chemistry

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Section: Synthesis and Characterizationsupporting

confidence: 66%

Mono- and dinuclear Pd(II) complexes of different salicylaldimine ligands as catalysts of transfer hydrogenation of nitrobenzene with cyclohexene and Suzuki–Miyaura coupling reactions

Taş

Kılıç

Durgun

et al. 2009

Journal of Organometallic Chemistry

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“…Complexes such as 13 or 14 are considered to be intermediates in the formation of inserted compounds such as 12 . ,,,, When 12 or 13 is reacted with another equivalent of the isocyanide, mixtures were obtained that we were not able to separate. However, from the complex mixture obtained by reacting 14 with another CNXy, the highly functionalized, stable ketenimine 15 (see Scheme ) could be isolated.…”

Section: Resultsmentioning

confidence: 99%

Palladium-Assisted Formation of Carbon−Carbon Bonds. 7.¹ Reactions of (2,3,4-Trimethoxy-6-X-phenyl)palladium Complexes with Alkynes (X = C(O)NHBu^t) and Isocyanides (X = C(O)NHBu^t, C(O)Me, CHO): Crystal and Molecular Structures of [Pd{C₆H{C(O)NHBu^t}-6-(OMe)₃-2,3,4}(bpy)](CF₃SO₃), [Pd{C(CO₂Me)C(CO₂Me)C₆H{C(O)NHBu^t}-6-(OMe)₃-2,3,4)}- Cl(PPh₃)], [Pd{C(NXy)C<

et al. 1997

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The mercuriation of 3,4,5-trimethoxy(N-tert-butylcarbamoyl)benzene with mercury(II) acetate and subsequent reaction with KCl leads to the formation of [Hg{C 6 The reaction of 2 with [PdCl 2 (MeCN) 2 ] and 2,2′-bipyridine (bpy) affords [Pd(C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4)Cl(bpy)] (3), which reacts with Tl(CF 3 SO 3 ) giving [Pd-{C 6 H{C(O)NHBu t }}(bpy)](CF 3 SO 3 ) (4). Complex 2 reacts with [PdCl 2 (MeCN) 2 ] and acetylenes RCtCR to give metallic palladium and the spirocyclic compound 10-(N-tert-butylcarbamoyl)-6,7-dimethoxy-1,2,3,4-tetraphenylspiro[4.5]-1,3,6,9-decatetraen-8-one (5) when R ) Ph or the monoinserted palladium complex [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}(µ-Cl)] 2 (6) when R ) CO 2 Me. By reaction of 6 with L (1:2) or PPh 3 and Tl(CF 3 SO 3 ) (1:4:2), the complexes [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}Cl(L)] (L ) PPh 3 (7), CNXy (8) (Xy ) 2,6-dimethylphenyl)) or [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)-NHBu t }-6-(OMe) 3 -2,3,4}(PPh 3 ) 2 ](CF 3 SO 3 ) (9) are obtained respectively. The reactions of 4 and of the related complexes [Pd{C 6 H{C(O)Me}-6-(OMe) 3 -2,3,4}(bpy)](CF 3 SO 3 ) (10) or [Pd-{C 6 H{C(O)H}-6-(OMe) 3 -2,3,4}(NCMe)(bpy)](CF 3 SO 3 ) (11) with CNXy have also been studied, the following compounds being isolated: [Pd{C(dNXy)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}-(bpy)](CF 3 SO 3 ) (12) [Pd{C 6 H{C(O)Me}-6-(OMe) 3 -2,3,4}(CNXy)(bpy)](CF 3 SO 3 ) (13), [Pd-{C 6 H{C(O)H}-6-(OMe) 3 -2,3,4}(CNXy)(bpy)](CF 3 SO 3 ) (14), and the ketenimine 2-(2,6dimethylphenyl)-1-(((2,6-dimethylphenyl)imino)methylene)-5,6,7-trimethoxy-3-oxoisoindoline (15). The structures of 4, 7, 12, and 15 have been determined by X-ray crystallography.

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“…Isocyanide insertion into Pd-C bonds has been extensively studied, [35][36][37] but mainly for complexes containing phosphine ligands. [38][39][40][41][42][43] We describe in this report, of which a preliminary account has already appeared, 44 the insertion of isocyanides into the Pd-Me bond of (NkN)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: 97%

“…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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Configuration of imino carbon palladated pyridine-2-carbaldimines. Crystal and molecular structure of trans-chlorobis(dimethylphenylphosphine)[(p-methoxyphenyl)imino](2-pyridyl)methyl]palladium(II)

Cited by 40 publications

References 2 publications

Mono- and dinuclear Pd(II) complexes of different salicylaldimine ligands as catalysts of transfer hydrogenation of nitrobenzene with cyclohexene and Suzuki–Miyaura coupling reactions

Mono- and dinuclear Pd(II) complexes of different salicylaldimine ligands as catalysts of transfer hydrogenation of nitrobenzene with cyclohexene and Suzuki–Miyaura coupling reactions

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

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