The reaction of the ligand 2,3-dicyano-5,6-di(2-pyridyl)-pyrazine, [(CN)2dpp], with Pd(OAc)2, in CH3CN leads to the formation of three novel complexes which were characterized by thermogravimetric analysis, single crystal and powder X-ray measurements, MALDI-TOF mass spectra, IR and UV–visible spectroscopy as well as electrochemistry. As established by crystallographic work, the complex of formula [(CN)2dppPd(OAc)2]⋅H2O (molar ratio ligand/Pd(II) 1:1; species 3) shows a single Pd(OAc)2 unit coordinated to each nitrogen of the two pyridyl (py) groups of [(CN)2dpp]. i.e. the “py-py” mode of coordination previously established for the analogs [(CN)2dppMCl2] (M = Pd(II), Pt(II)). The second isolated species is a highly insoluble dinuclear Pd(II) complex of formula [(CN)2dpp{Pd(OAc)2}2]⋅5H2O (molar ratio ligand/Pd(II) 1:2; species 1), where the two Pd(OAc)2 units are each coordinated to one pyrazine nitrogen and one N atom of a pyridyl group on [(CN)2dpp] (“py-pyz” binding). Based on crystallographic work, the third isolated species is assigned the formula [(CN)(CONH)dppPd(OAc)] (molar ratio ligand/Pd(II) 1:1; species 2), which is formed by hydrolysis of a CN substituent on [(CN)2dpp] giving a –CONH- group and characterized by a “py-pyz” type of coordination. Electrochemical and spectroelectrochemical data of complexes 1, 2, and 3 in DMF and DMSO were used to assign the sites of electron transfer.

Multiple established forms of palladium acetate binding to the four N-atom donor 2,3-dicyano-5,6-di(2-pyridyl)-pyrazine, [(CN)2dpp] / Donzello, Maria Pia; Ercolani, C; Fang, Yuanyuan; Osterloh, Ryan W; Rizzoli, Corrado; Viola, Elisa; Stuzhin, Pavel A; Kadish, Karl M.. - In: INORGANICA CHIMICA ACTA. - ISSN 0020-1693. - 534:(2022). [10.1016/j.ica.2021.120773]

Multiple established forms of palladium acetate binding to the four N-atom donor 2,3-dicyano-5,6-di(2-pyridyl)-pyrazine, [(CN)2dpp]

Donzello, Maria Pia
;
Ercolani, C;Viola, Elisa;
2022

Abstract

The reaction of the ligand 2,3-dicyano-5,6-di(2-pyridyl)-pyrazine, [(CN)2dpp], with Pd(OAc)2, in CH3CN leads to the formation of three novel complexes which were characterized by thermogravimetric analysis, single crystal and powder X-ray measurements, MALDI-TOF mass spectra, IR and UV–visible spectroscopy as well as electrochemistry. As established by crystallographic work, the complex of formula [(CN)2dppPd(OAc)2]⋅H2O (molar ratio ligand/Pd(II) 1:1; species 3) shows a single Pd(OAc)2 unit coordinated to each nitrogen of the two pyridyl (py) groups of [(CN)2dpp]. i.e. the “py-py” mode of coordination previously established for the analogs [(CN)2dppMCl2] (M = Pd(II), Pt(II)). The second isolated species is a highly insoluble dinuclear Pd(II) complex of formula [(CN)2dpp{Pd(OAc)2}2]⋅5H2O (molar ratio ligand/Pd(II) 1:2; species 1), where the two Pd(OAc)2 units are each coordinated to one pyrazine nitrogen and one N atom of a pyridyl group on [(CN)2dpp] (“py-pyz” binding). Based on crystallographic work, the third isolated species is assigned the formula [(CN)(CONH)dppPd(OAc)] (molar ratio ligand/Pd(II) 1:1; species 2), which is formed by hydrolysis of a CN substituent on [(CN)2dpp] giving a –CONH- group and characterized by a “py-pyz” type of coordination. Electrochemical and spectroelectrochemical data of complexes 1, 2, and 3 in DMF and DMSO were used to assign the sites of electron transfer.
2022
mono/dinuclear Pd(II) complexes; Py-py/py-pyz binding; rare exclusive Pd(II) coordination sites
01 Pubblicazione su rivista::01a Articolo in rivista
Multiple established forms of palladium acetate binding to the four N-atom donor 2,3-dicyano-5,6-di(2-pyridyl)-pyrazine, [(CN)2dpp] / Donzello, Maria Pia; Ercolani, C; Fang, Yuanyuan; Osterloh, Ryan W; Rizzoli, Corrado; Viola, Elisa; Stuzhin, Pavel A; Kadish, Karl M.. - In: INORGANICA CHIMICA ACTA. - ISSN 0020-1693. - 534:(2022). [10.1016/j.ica.2021.120773]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/1641588
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