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-

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)

“…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 ).…”

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)

“…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 ).…”

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

“…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 .…”

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

“…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.…”

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)

“…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 ).…”

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

“…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 .…”

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

“…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.…”

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)

“…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 ).…”

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

“…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 .…”

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

“…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.…”