Synthesis and Structure of an Asymmetric Binuclear Phenylhydrazonato Anionic Complex of Palladium Containing a Pd−C(aryl) Bondcis to a Pd−N(amido) Bond

Carbayo, Arancha; Cuevas, José V.; Garcı́a-Herbosa, Gabriel; Garcı́a-Granda, Santiago; Miguel, Daniel

doi:10.1002/1099-0682(200109)2001:9<2361::aid-ejic2361>3.0.co;2-4

Cited by 16 publications

(3 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The isocyanide is in cis position with respect to the aryl ligand. This geometry is in agreement with the greater transphobia between two carbon donor ligands than between a C and an N donor ligand . In the asymmetric unit, molecules of 3d associate through intermolecular N−H···Br hydrogen bonds (see Table ), forming ribbons parallel to the x axis (Figure ).…”

Section: Resultssupporting

confidence: 72%

Palladium-Assisted Formation of Carbon−Carbon Bonds. Part 10.¹ Insertion Reactions of Isocyanides into the Pd−C Bond of Orthopalladated Primary Amines. Synthesis of 2-R-Aminoisoindolinium Salts (R = ^tBu, 2,6-Xylyl)

et al. 2002

View full text Add to dashboard Cite

The palladated primary amines [Pd{C 6 H 3 CH 2 NH 2 -2-X-5}(µ-Br)] 2 [X ) H (1a), OMe (1b), NO 2 (1c), F (1d)] react with isocyanides (Pd:RNC ) 1:1) to give [Pd{C 6 When XyNC reacts with 1a (Pd:RNC ) 1:2) or with 2a (Pd:RNC ) 1:1), the complex [Pd{(CdNXy)C 6 H 4 CH 2 NH 2 -2}(XyNC)Br] (4a) is obtained. The reactions of complexes 1 with isocyanides in the ratio Pd:RNC ) 1:3 lead to Pd(I) complexes [Pd 2 Br 2 L 4 ] [L ) XyNC (5); L ) t Bu ( 6)]. On the basis of NMR data we propose the following reaction pathway for this reduction process: (1) formation of the corresponding monomer 2 or 3, (2) insertion of one molecule of the isocyanide into the Pd-C bond of 2 or 3 to give [Pd{(CdNR)C 6 H 3 CH 2 NH 2 -2-X-5}(RNC)Br], (3) cleavage of the N-Pd bond and coordination of a new isocyanide molecule to give complexes [Pd{(CdNR)C 6 H 3 CH 2 NH 2 -2-X-5}(RNC) 2 Br][detected in solution for R ) Xy, X ) H (7a) and isolated as an acetylated derivative of this complex [Pd{(CdNXy)C 6 H 4 CH 2 NHC(O)Me-2}(XyNC) 2 Br] (8a)], and (4) decomposition of these complexes to give 5 or 6. The organic product of these reactions was not identified. By refluxing mixtures of complexes 1 with RNC and TlOTf (Pd:RNC:TfO ) 1:1:1) the corresponding isoindolinium triflates 9‚OTf [R ) Xy, X ) H (9a‚OTf), OMe (9b‚OTf), F (9d‚OTf)] or 10‚OTf [R ) t Bu, X ) H (10a‚OTf), OMe (10b‚OTf), F (10d‚OTf)] were isolated and characterized. A mechanism of formation of these isoindolinium triflates is proposed. When the reaction between 1a and XyNC (Pd:RNC ) 1:1) was carried out in refluxing toluene in the absence of TlOTf, or when 2a was refluxed in toluene, an insertion of the isocyanide occurs in both cases to give [Pd{(CdNXy)C 6 H 4 CH 2 NH 2 -2}Br] 2 (11). If 1a or 2a is reacted with XyNC (Pd:RNC ) 1:1.25 or 1:0.25, respectively), the complex [PdBr 2 {2-(XyNH)-isoindole} 2 ] (12) is formed. A proposal for the reaction pathway of this process is discussed. The crystal structures of 3d, 9a‚OTf, and 12 have been determined.

show abstract

Section: Resultssupporting

confidence: 72%

Palladium-Assisted Formation of Carbon−Carbon Bonds. Part 10.¹ Insertion Reactions of Isocyanides into the Pd−C Bond of Orthopalladated Primary Amines. Synthesis of 2-R-Aminoisoindolinium Salts (R = ^tBu, 2,6-Xylyl)

et al. 2002

View full text Add to dashboard Cite

show abstract

“…It is generally less marked for Pt(II) than for Pd(II). We have named this destabilizing effect transphobia ( T ), a term that has already been accepted by many authors. − ,− When the product of a reaction contains a pair of ligands with high T in trans positions, one of which is generally a C-donor, a further reaction such as an X−Y coupling process (X = C, Y = C, N, O, P), ,,,, an insertion of atmospheric O 2 into the C−Pd bond, , or an intramolecular redox reaction usually takes place. , In contrast, if the two pairs of trans ligands have low T , the reaction product tends to be stable. Although the observation of the geometries of stable complexes cannot always provide information on the degree of T of their possible pairs of trans ligands, we think that looking at the geometry of a family of complexes would allow more members to be placed in the scale of T .…”

Section: Resultsmentioning

confidence: 99%

Study of the Reactivity of 2-Acetyl-, 2-Cyano-, 2-Formyl-, and 2-Vinylphenyl Palladium(II) Complexes. Mono- and Triinsertion of an Isocyanide into the Pd−C Bond. A 2-Cyanophenyl Palladium Complex as a Ligand

et al. 2002

View full text Add to dashboard Cite

We have studied the reactivity of the complexes [Pd(C6H4X-2)Br(bpy)] (bpy = 2,2‘-bipyridine; X = C(O)Me (1a), CN (1b), CHO (1c)), [Pd{C6H4CHCH2-2}(PPh3)(bpy)](TfO) (TfO = CF3SO3; 2d), trans-[Pd(C6H4X-2)Br(PPh3)2] (X = C(O)Me (3a), CN (3b), CHCH2 (3d)), and [Pd(μ-Br)(C6H4X-2)(PPh3)]2(X = C(O)Me (4a), CN (4b)). Their reactions with XyNC (Xy = 2,6-dimethylphenyl) depend on the nature of X and the other ligands and on the reaction conditions. The products of these reactions are mono- and triinserted complexes. Among the former are [Pd{C(NXy)C6H4X-2}Br(L2)] (L2 = bpy, X = C(O)Me (5a), CN (5b); L = CNXy, X = C(O)Me (6a), CN (6b), CHCH2 (6d)) and trans-[Pd{C(NXy)C6H4CHCH2-2}(CNXy)2(PPh3)](TfO) (7d). The reaction of 1c with XyNC (1:5 molar ratio) gives 10, a product resulting after substitution of bpy, coordination of two molecules of XyNC, triinsertion of XyNC, and a cyclization resulting after the attack of the nitrogen of the first inserted molecule at the carbon atom of the formyl group. The complexes [Pd{κ2 C 1,N 3-C(NXy)C(NXy)C(NXy)C6H4X-2}Br(CNXy)] (X = C(O)Me (8a), CN (8b)) were obtained by reacting (i) 3a or 3b with XyNC (1:4 molar ratio) or (ii) Pd(dba)2 (dba = dibenzylideneacetone) with BrC6H4X-2 and XyNC (1:1:4 molar ratio). When this oxidative addition reaction was carried out with BrC6H4CHO-2, the resulting product decomposed to give the Pd(I) complex [Pd2Br2(CNXy)4] (9). Tl(TfO) was reacted with (i) 8a and 8b (1:1 molar ratio) to give the corresponding triflato complexes 11a and 11b, (ii) 4a (1:2 molar ratio) in the presence of moisture to give the cyclopalladated aquo complex [Pd{κ2 C,O-C6H4{C(O)Me-2}(OH2)(PPh3)](TfO) (12a), and (iii) 4b (3:1 molar ratio) to give [Pd(C6H4CN-2)(κ2 N,N- 4b)(PPh3)](TfO) (13b), in which 4b behaves as a ligand through the two cyano groups. The crystal structures of 5b, 6b, 7d, 8a,b, 9, 10, 11a,b, 12a, and 13b have been determined by X-ray diffraction studies.

show abstract

“…A pesar de la falta de correspondencia entre los átomos "blando" de Pd (II) y "duro" de N (amido) del principio HSAB de Pearson, complejos de paladio que contienen terminal de Pd-N amido enlaces han sido bien caracterizado en muchos casos. [109][110][111][112][113][114][115][116][117][118][119][120][121] Ilustración 69: Esquema del primer paso en la síntesis del complejo 6.…”

Section: Comentarios Mecanísticos a Los Resultados Experimentalesunclassified

Síntesis, reactividad, estructura y propiedades de compuestos de metales del grupo del platino con enlaces M-N amido, amino e imino. ataques nucleofílicos sobre iminas coordinadas a paladio

Birkle¹

View full text Add to dashboard Cite

Caracterización cristalográfica de [Pd(acac)(C 5 H 4 NCH{NH-C 6 H 4-2-CH 3 }C(COCH 3) 2)] (6b) ........ 6.4 Caracterización cristalográfica de [Pd(acac)(C 5 H 4 NCH{NH-C 6 H 3-2,6-(CH 3) 2 }C(COCH 3) 2)] (6c). 6.5 Caracterización cristalográfica de [Pd(acac)(C 5 H 4 NCH{NH-C 6 H 4-2-iPr}C(COCH 3) 2)] (6d) .......... 6.6 Caracterización cristalográfica de [Pd(acac)(C 5 H 4 NCH{NH-C 6 H 4-4-OCH 3 }C(COCH 3) 2)] (6f) ...... 6.7 Caracterización cristalográfica de [Pd(acac)(C 5 H 4 NCH{NH-C 6 H 4-4-CF 3 }C(COCH 3) 2)] (6h) ......... 6.8 Caracterización cristalográfica de [Pd(acac)(Ph 2 P-C 5 H 4 N-CH{NH-C 6 H 4-R}C(COCH 3) 2)] (7a) ..... 6.9 Caracterización cristalográfica de [PdCl(pip)(NC 5 H 4 {NH-C 6 H 4-4-OCH 3 }C(COCH 3) 2)] (8f) .......... 6.10 Caracterización cristalográfica de [PdCl(pip)(NC 5 H 4 {NH-C 6 H 4-2-iPr]}C(COCH 3) 2)] (9d) .

show abstract

Synthesis and Structure of an Asymmetric Binuclear Phenylhydrazonato Anionic Complex of Palladium Containing a Pd−C(aryl) Bondcis to a Pd−N(amido) Bond

Abstract: Keywords: Palladium / Hydrazones / Cyclopalladatation / Amido compoundsThe synthesis and structure of a unique asymmetric folded binuclear anionic complex of palladium containing two dif-

Cited by 16 publications

References 14 publications

Palladium-Assisted Formation of Carbon−Carbon Bonds. Part 10.¹ Insertion Reactions of Isocyanides into the Pd−C Bond of Orthopalladated Primary Amines. Synthesis of 2-R-Aminoisoindolinium Salts (R = ^tBu, 2,6-Xylyl)

Palladium-Assisted Formation of Carbon−Carbon Bonds. Part 10.¹ Insertion Reactions of Isocyanides into the Pd−C Bond of Orthopalladated Primary Amines. Synthesis of 2-R-Aminoisoindolinium Salts (R = ^tBu, 2,6-Xylyl)

Study of the Reactivity of 2-Acetyl-, 2-Cyano-, 2-Formyl-, and 2-Vinylphenyl Palladium(II) Complexes. Mono- and Triinsertion of an Isocyanide into the Pd−C Bond. A 2-Cyanophenyl Palladium Complex as a Ligand

Síntesis, reactividad, estructura y propiedades de compuestos de metales del grupo del platino con enlaces M-N amido, amino e imino. ataques nucleofílicos sobre iminas coordinadas a paladio

Contact Info

Product

Resources

About

Synthesis and Structure of an Asymmetric Binuclear Phenylhydrazonato Anionic Complex of Palladium Containing a Pd−C(aryl) Bondcis to a Pd−N(amido) Bond

Abstract: Keywords: Palladium / Hydrazones / Cyclopalladatation / Amido compoundsThe synthesis and structure of a unique asymmetric folded binuclear anionic complex of palladium containing two dif-

Cited by 16 publications

References 14 publications

Palladium-Assisted Formation of Carbon−Carbon Bonds. Part 10.1 Insertion Reactions of Isocyanides into the Pd−C Bond of Orthopalladated Primary Amines. Synthesis of 2-R-Aminoisoindolinium Salts (R = tBu, 2,6-Xylyl)

Palladium-Assisted Formation of Carbon−Carbon Bonds. Part 10.1 Insertion Reactions of Isocyanides into the Pd−C Bond of Orthopalladated Primary Amines. Synthesis of 2-R-Aminoisoindolinium Salts (R = tBu, 2,6-Xylyl)

Study of the Reactivity of 2-Acetyl-, 2-Cyano-, 2-Formyl-, and 2-Vinylphenyl Palladium(II) Complexes. Mono- and Triinsertion of an Isocyanide into the Pd−C Bond. A 2-Cyanophenyl Palladium Complex as a Ligand

Síntesis, reactividad, estructura y propiedades de compuestos de metales del grupo del platino con enlaces M-N amido, amino e imino. ataques nucleofílicos sobre iminas coordinadas a paladio

Contact Info

Product

Resources

About

Palladium-Assisted Formation of Carbon−Carbon Bonds. Part 10.¹ Insertion Reactions of Isocyanides into the Pd−C Bond of Orthopalladated Primary Amines. Synthesis of 2-R-Aminoisoindolinium Salts (R = ^tBu, 2,6-Xylyl)

Palladium-Assisted Formation of Carbon−Carbon Bonds. Part 10.¹ Insertion Reactions of Isocyanides into the Pd−C Bond of Orthopalladated Primary Amines. Synthesis of 2-R-Aminoisoindolinium Salts (R = ^tBu, 2,6-Xylyl)