Synthesis and crystal structure of some (2,2′-dipyridylamine)(carboxylato)(phenoxo)copper(II) complexes with rather unusual phenoxo ligands

Facchinetti, Alessandro; Marsich, N.; Camus, A.; Ugozzoli, Franco; Massera, Chiara; Lanfredi, Anna Maria Manotti

doi:10.1016/s0020-1693(01)00571-0

Cited by 6 publications

(2 citation statements)

References 33 publications

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“…Only one structurally characterized diruthenium complex, encompassing the bridging dipyridylamine ligand, has been reported so far . However, the nonplanarity of the coordinated terminal dipyridylamine ligand was evidenced previously in other structurally characterized metal complexes …”

Section: Resultsmentioning

confidence: 95%

Stepwise Synthesis of [Ru(trpy)(L)(X)]ⁿ⁺ (trpy = 2,2‘:6‘,2‘ ‘-Terpyridine; L = 2,2‘-Dipyridylamine; X = Cl^-, H₂O, NO₂^-, NO⁺, O²^-). Crystal Structure, Spectral, Electron-Transfer, and Photophysical Aspects

et al. 2003

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Ruthenium−terpyridine complexes incorporating a 2,2′-dipyridylamine ancillary ligand [Ru II (trpy)(L)(X)](ClO 4 ) n [trpy ) 2,2′:6′,2′′-terpyridine; L ) 2,2′-dipyridylamine; and X ) 4)] were synthesized in a stepwise manner starting from Ru III (trpy)(Cl) 3 . The single-crystal X-ray structures of all of the four members (1−4) were determined. The Ru(III)/Ru(II) couple of 1 and 3 appeared at 0.64 and 0.88 V versus the saturated calomel electrode in acetonitrile. The aqua complex 2 exhibited a metalbased couple at 0.48 V in water, and the potential increased linearly with the decrease in pH. The electron−proton content of the redox process over the pH range of 6.8−1.0 was calculated to be a 2e -/1H + process. However, the chemical oxidation of 2 by an aq Ce(IV) solution in 1 N H 2 SO 4 led to the direct formation of corresponding oxo species [Ru IV (trpy)(L)(O)] 2+ via the concerted 2e -/2H + oxidation process. The two successive reductions of the coordinated nitrosyl function of 4 appeared at +0.34 and −0.34 V corresponding to Ru II −NO + f Ru II −NO • and Ru II −NO • f Ru II −NO -, respectively. The one-electron-reduced Ru II −NO • species exhibited a free-radical electron paramagnetic resonance signal at g ) 1.990 with nitrogen hyperfine structures at 77 K. The NO stretching frequency of 4 (1945 cm -1 ) was shifted to 1830 cm -1 in the case of [Ru II (trpy)(L)(NO • )] 2+ . In aqueous solution, the nitrosyl complex 4 slowly transformed to the nitro derivative 3 with the pseudo-first-order rate constant of k 298 /s -1 ) 1.7 × 10 -4 . The chloro complex 1 exhibited a dual luminescence at 650 and 715 nm with excited-state lifetimes of 6 and 1 µs, respectively.

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Section: Resultsmentioning

confidence: 95%

Stepwise Synthesis of [Ru(trpy)(L)(X)]ⁿ⁺ (trpy = 2,2‘:6‘,2‘ ‘-Terpyridine; L = 2,2‘-Dipyridylamine; X = Cl^-, H₂O, NO₂^-, NO⁺, O²^-). Crystal Structure, Spectral, Electron-Transfer, and Photophysical Aspects

et al. 2003

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“…Many of these examples feature interactions with solvent molecules (dichloromethane or chloroform), but restricting the search further to include only Fe−Cl contacts between first row transition metals and aryl chlorides returned 20 published structures. The M−Cl distances in these complexes extend from 2.30 Å to 3.09 Å, [15–23] indicating that the Fe−Cl interaction in ( Cl2Ph PDP Ph )Fe(OEt 2 ) falls right in the center of this range. The only reported examples for iron exhibit Fe−Cl distances of 2.31 Å 15 and 2.73 Å [16] …”

Section: Resultsmentioning

confidence: 96%

Effects of 2,6‐Dichlorophenyl Substituents on the Coordination Chemistry of Pyridine Dipyrrolide Iron Complexes

Hakey

Leary

Rodríguez

et al. 2021

Zeitschrift anorg allge chemie

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A series of iron complexes featuring the pyridine dipyrrolide (PDP) pincer ligand [Cl2PhPDPPh]2−, obtained via deprotonation of 2,6‐bis(5‐(2,6‐dichlorophenyl)‐3‐phenyl‐1H‐pyrrol‐2‐yl)pyridine, H2Cl2PhPDPPh, is reported and structurally and spectroscopically characterized. While the bis‐pyridine adduct (Cl2PhPDPPh)Fe(py)2 exhibits nearly identical features as previously reported (MesPDPPh)Fe(py)2 (H2MesPDPPh=2,6‐bis(5‐(2,4,6‐trimethylphenyl)‐3‐phenyl‐1H‐pyrrol‐2‐yl)pyridine), the diethyl ether and tetrahydrofuran adducts (Cl2PhPDPPh)Fe(OEt2) and (Cl2PhPDPPh)Fe(thf) show additional weak Fe−Cl interactions that impact the overall coordination geometries and result in strong deviations from planar coordination environments. The reaction of (Cl2PhPDPPh)Fe(thf) with 1‐adamantyl azide provided the isolable iron imido complex (Cl2PhPDPPh)Fe(N1Ad), highlighting the improved stability of [Cl2PhPDPPh]2− towards intramolecular nitrene group transfer from the high‐valent iron‐imido unit. The electronic structure of (Cl2PhPDPPh)Fe(N1Ad) was investigated by density functional theory (DFT) and complete active space self‐consistent field (CASSCF) calculations. These computational studies suggest energetically close‐lying diamagnetic and paramagnetic states and help to conceptualize the unusual magnetic properties of the complex observed by variable‐temperature 1H NMR spectroscopy.

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Reactions between Cu(II) halide complexes of 2,2′-dipyridylamine and nitrophenolates. X-ray diffraction structure of the [bis(2,2′-dipyridylamine)di(p-nitrophenolato)di(μ-methoxo)dicopper(II)], [Cu(dipyam)(pnp)(μ-OCH3)]2, a dimeric complex containing axial phenoxo ligands in square-pyramidal arrangements

Camus

Facchinetti

Marsich

et al. 2003

Inorganica Chimica Acta

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Synthesis and crystal structure of some (2,2′-dipyridylamine)(carboxylato)(phenoxo)copper(II) complexes with rather unusual phenoxo ligands

Cited by 6 publications

References 33 publications

Stepwise Synthesis of [Ru(trpy)(L)(X)]ⁿ⁺ (trpy = 2,2‘:6‘,2‘ ‘-Terpyridine; L = 2,2‘-Dipyridylamine; X = Cl^-, H₂O, NO₂^-, NO⁺, O²^-). Crystal Structure, Spectral, Electron-Transfer, and Photophysical Aspects

Stepwise Synthesis of [Ru(trpy)(L)(X)]ⁿ⁺ (trpy = 2,2‘:6‘,2‘ ‘-Terpyridine; L = 2,2‘-Dipyridylamine; X = Cl^-, H₂O, NO₂^-, NO⁺, O²^-). Crystal Structure, Spectral, Electron-Transfer, and Photophysical Aspects

Effects of 2,6‐Dichlorophenyl Substituents on the Coordination Chemistry of Pyridine Dipyrrolide Iron Complexes

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Synthesis and crystal structure of some (2,2′-dipyridylamine)(carboxylato)(phenoxo)copper(II) complexes with rather unusual phenoxo ligands

Cited by 6 publications

References 33 publications

Stepwise Synthesis of [Ru(trpy)(L)(X)]n+ (trpy = 2,2‘:6‘,2‘ ‘-Terpyridine; L = 2,2‘-Dipyridylamine; X = Cl-, H2O, NO2-, NO+, O2-). Crystal Structure, Spectral, Electron-Transfer, and Photophysical Aspects

Stepwise Synthesis of [Ru(trpy)(L)(X)]n+ (trpy = 2,2‘:6‘,2‘ ‘-Terpyridine; L = 2,2‘-Dipyridylamine; X = Cl-, H2O, NO2-, NO+, O2-). Crystal Structure, Spectral, Electron-Transfer, and Photophysical Aspects

Effects of 2,6‐Dichlorophenyl Substituents on the Coordination Chemistry of Pyridine Dipyrrolide Iron Complexes

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Stepwise Synthesis of [Ru(trpy)(L)(X)]ⁿ⁺ (trpy = 2,2‘:6‘,2‘ ‘-Terpyridine; L = 2,2‘-Dipyridylamine; X = Cl^-, H₂O, NO₂^-, NO⁺, O²^-). Crystal Structure, Spectral, Electron-Transfer, and Photophysical Aspects

Stepwise Synthesis of [Ru(trpy)(L)(X)]ⁿ⁺ (trpy = 2,2‘:6‘,2‘ ‘-Terpyridine; L = 2,2‘-Dipyridylamine; X = Cl^-, H₂O, NO₂^-, NO⁺, O²^-). Crystal Structure, Spectral, Electron-Transfer, and Photophysical Aspects