The First Transition Metal Complexes of 15-Membered Triolefinic Macrocycles: (E,E,E)-1,6,11-Tris(arenesulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-triene Complexes of Palladium(0), Platinum(0), and Silver(I)

Syntheses, Structures and Redox Properties of New Macrocyclic Triazatriolefinic Pd0 Complexes and Their Polypyrrole Modified Electrodes − Application to Heterogeneous Catalytic Suzuki Cross‐Coupling Reactions

“…The central point of the olefins and the palladium are all nearly situated in the same plane and thus the coordination of the palladium is slightly distorted trigonal planar. Bond lengths and angles are within the expected ranges for this type of complex 12b. The three nitrogen atoms of the sulfonamides (N1, N2, N3) and the palladium center are also situated very close to a plane which will from now on be referred to as the main plane.…”

Syntheses, Structures and Redox Properties of New Macrocyclic Triazatriolefinic Pd0 Complexes and Their Polypyrrole Modified Electrodes − Application to Heterogeneous Catalytic Suzuki Cross‐Coupling Reactions

“…The central point of the olefins and the palladium are all nearly situated in the same plane and thus the coordination of the palladium is slightly distorted trigonal planar. Bond lengths and angles are within the expected ranges for this type of complex 12b. The three nitrogen atoms of the sulfonamides (N1, N2, N3) and the palladium center are also situated very close to a plane which will from now on be referred to as the main plane.…”

15‐Membered Triolefinic Macrocycles − Catalytic Role of (E,E,E)‐1,6,11‐Tris(arenesulfonyl)‐1,6,11‐triazacyclopentadeca‐3,8,13‐triene Complexes of Palladium(0) in the Presence of Phosphanes

“…Upon addition of two mol of triphenylphosphane (with respect to Pd), however, the colorless solution turned yellow, the 19 F NMR signal of free macrocycle 1a appeared while that of complex 2a disappeared, and the 31 P NMR spectrum showed a broad peak centered at δ ϭ 10 ppm, assigned to species Pd(PPh 3 ) n in fast equilibrium. After 24 hours the reaction was complete, 19 Table 4), or only 3a (Entry 3), or Pd 2 (dba) 3 plus two mol of triphenylphosphane (Entry 4) gave similar results in terms of the intermediates involved. Indeed, three to four singlets were detected in the 31 P NMR spectra in all three cases.…”

“…We chose 31 P and 19 F NMR and electrospray ionization mass spectrometry as analytical tools to determine the fates of ligand 1, complex 2, and of ancillary phosphanes in the experiments to follow. In these experiments we have studied:…”

Palladium(0) Nanoparticles Stabilized by Phosphorus Dendrimers Containing Coordinating 15-Membered Triolefinic Macrocycles in Periphery

“…The presence or the absence of palladium(0) coordinated to the macrocycle can be deduced from the NMR spectra. Indeed, free macrocycles present signals for the olefinic protons and carbons at δ ∼5.50−5.80 and ∼124 ppm, respectively, whereas for palladium complexes strong upfield shifts are observed up to δ 2.50−4.40 (depending on the proton considered) and 78−83 ppm, respectively …”

Syntheses, Structures and Redox Properties of New Macrocyclic Triazatriolefinic Pd0 Complexes and Their Polypyrrole Modified Electrodes − Application to Heterogeneous Catalytic Suzuki Cross‐Coupling Reactions

“…The central point of the olefins and the palladium are all nearly situated in the same plane and thus the coordination of the palladium is slightly distorted trigonal planar. Bond lengths and angles are within the expected ranges for this type of complex 12b. The three nitrogen atoms of the sulfonamides (N1, N2, N3) and the palladium center are also situated very close to a plane which will from now on be referred to as the main plane.…”

15‐Membered Triolefinic Macrocycles − Catalytic Role of (E,E,E)‐1,6,11‐Tris(arenesulfonyl)‐1,6,11‐triazacyclopentadeca‐3,8,13‐triene Complexes of Palladium(0) in the Presence of Phosphanes

“…Upon addition of two mol of triphenylphosphane (with respect to Pd), however, the colorless solution turned yellow, the 19 F NMR signal of free macrocycle 1a appeared while that of complex 2a disappeared, and the 31 P NMR spectrum showed a broad peak centered at δ ϭ 10 ppm, assigned to species Pd(PPh 3 ) n in fast equilibrium. After 24 hours the reaction was complete, 19 Table 4), or only 3a (Entry 3), or Pd 2 (dba) 3 plus two mol of triphenylphosphane (Entry 4) gave similar results in terms of the intermediates involved. Indeed, three to four singlets were detected in the 31 P NMR spectra in all three cases.…”

“…We chose 31 P and 19 F NMR and electrospray ionization mass spectrometry as analytical tools to determine the fates of ligand 1, complex 2, and of ancillary phosphanes in the experiments to follow. In these experiments we have studied:…”

Palladium(0) Nanoparticles Stabilized by Phosphorus Dendrimers Containing Coordinating 15-Membered Triolefinic Macrocycles in Periphery

“…The presence or the absence of palladium(0) coordinated to the macrocycle can be deduced from the NMR spectra. Indeed, free macrocycles present signals for the olefinic protons and carbons at δ ∼5.50−5.80 and ∼124 ppm, respectively, whereas for palladium complexes strong upfield shifts are observed up to δ 2.50−4.40 (depending on the proton considered) and 78−83 ppm, respectively …”

Syntheses, Structures and Redox Properties of New Macrocyclic Triazatriolefinic Pd0 Complexes and Their Polypyrrole Modified Electrodes − Application to Heterogeneous Catalytic Suzuki Cross‐Coupling Reactions

“…The central point of the olefins and the palladium are all nearly situated in the same plane and thus the coordination of the palladium is slightly distorted trigonal planar. Bond lengths and angles are within the expected ranges for this type of complex 12b. The three nitrogen atoms of the sulfonamides (N1, N2, N3) and the palladium center are also situated very close to a plane which will from now on be referred to as the main plane.…”

15‐Membered Triolefinic Macrocycles − Catalytic Role of (E,E,E)‐1,6,11‐Tris(arenesulfonyl)‐1,6,11‐triazacyclopentadeca‐3,8,13‐triene Complexes of Palladium(0) in the Presence of Phosphanes

“…Upon addition of two mol of triphenylphosphane (with respect to Pd), however, the colorless solution turned yellow, the 19 F NMR signal of free macrocycle 1a appeared while that of complex 2a disappeared, and the 31 P NMR spectrum showed a broad peak centered at δ ϭ 10 ppm, assigned to species Pd(PPh 3 ) n in fast equilibrium. After 24 hours the reaction was complete, 19 Table 4), or only 3a (Entry 3), or Pd 2 (dba) 3 plus two mol of triphenylphosphane (Entry 4) gave similar results in terms of the intermediates involved. Indeed, three to four singlets were detected in the 31 P NMR spectra in all three cases.…”

“…We chose 31 P and 19 F NMR and electrospray ionization mass spectrometry as analytical tools to determine the fates of ligand 1, complex 2, and of ancillary phosphanes in the experiments to follow. In these experiments we have studied:…”

Palladium(0) Nanoparticles Stabilized by Phosphorus Dendrimers Containing Coordinating 15-Membered Triolefinic Macrocycles in Periphery

“…The presence or the absence of palladium(0) coordinated to the macrocycle can be deduced from the NMR spectra. Indeed, free macrocycles present signals for the olefinic protons and carbons at δ ∼5.50−5.80 and ∼124 ppm, respectively, whereas for palladium complexes strong upfield shifts are observed up to δ 2.50−4.40 (depending on the proton considered) and 78−83 ppm, respectively …”