Coordination Structure Conversion of Hydrazone-Palladium(II) Complexes in the Solid State and in Solution

Fumi Kitamura, Kana Sawaguchi, Asami Mori, Shoji Takagi, Takayoshi Suzuki, Atsushi Kobayashi, Masako Kato, Kiyohiko Nakajima

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Abstract

We prepared hydrazone-palladium(II) complexes of [PdCl2(HLn)] and [PdCl(Ln)] (n = 1-3) by the reaction of [PdCl2(cod)] or [PdCl2(PhCN)2] and the hydrazone ligands of HLn {N′-(pyridin-2-ylmethylene)picolinohydrazide (HL1), N′-[1-(pyridin-2-yl)ethylidene]picolinohydrazide (HL2), and N′-[(6-methylpyridin-2-yl)methylene]picolinohydrazide (HL3)}. The structures of the complexes were determined by X-ray analysis. The hydrazone ligands had κN(py1),κN(imine) and κN(amidate),κN(py2) bidentate coordination modes in [PdCl2(HLn)] (1, n = 1; 2, n = 2) and in [PdCl2(HL3)] (3), respectively. In contrast, tridentate coordination modes of κN(py1),κN(imine),κN(py2) and κN(py1),κN(amidate),κN(py2) were observed in [PdCl(Ln)] (4, n = 1; 5, n = 2) and in [PdCl(Ln)] (6, n = 1; 7, n = 2; 8, n = 3). Thermal conversion of complexes 1-3 to complexes 6-8 proceeded in acetonitrile. Complexes 4 and 5 were obtained from complexes 1 and 2, respectively, in a basic acetonitrile solution under dark conditions. Complex 4 reverted immediately to complex 1 in an acidic acetonitrile solution that included hydrochloric acid. However, under room light, in the basic acetonitrile solution that included trimethylamine, complex 4 converted photochemically to complex 6. The thermochromic or vapochromic structure conversion of these complexes also occurred in the solid state. On heating at 180 °C, the color of the crystals of complexes 1, 2, and 3 changed from yellow to orange in the solid state. 1H NMR and/or UV-vis absorption spectroscopy confirmed that the orange complexes 6-8 were produced. The reddish-orange crystals of complexes 4 and 5 were exposed to hydrogen chloride vapor to yield the yellow products of complexes 1 and 2, respectively. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)8436-8448
Number of pages13
JournalInorganic Chemistry
Volume54
Issue number17
DOIs
Publication statusPublished - Sep 8 2015

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Hydrazones
hydrazones
Palladium
acetonitrile
palladium
solid state
imines
Imines
Hydrochloric Acid
ligands
hydrogen chlorides
hydrochloric acid
methylene
crystals
rooms
absorption spectroscopy
Ligands
Crystals
vapors
color

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Coordination Structure Conversion of Hydrazone-Palladium(II) Complexes in the Solid State and in Solution. / Kitamura, Fumi; Sawaguchi, Kana; Mori, Asami; Takagi, Shoji; Suzuki, Takayoshi; Kobayashi, Atsushi; Kato, Masako; Nakajima, Kiyohiko.

In: Inorganic Chemistry, Vol. 54, No. 17, 08.09.2015, p. 8436-8448.

Research output: Contribution to journalArticle

Kitamura, F, Sawaguchi, K, Mori, A, Takagi, S, Suzuki, T, Kobayashi, A, Kato, M & Nakajima, K 2015, 'Coordination Structure Conversion of Hydrazone-Palladium(II) Complexes in the Solid State and in Solution', Inorganic Chemistry, vol. 54, no. 17, pp. 8436-8448. https://doi.org/10.1021/acs.inorgchem.5b01128
Kitamura, Fumi ; Sawaguchi, Kana ; Mori, Asami ; Takagi, Shoji ; Suzuki, Takayoshi ; Kobayashi, Atsushi ; Kato, Masako ; Nakajima, Kiyohiko. / Coordination Structure Conversion of Hydrazone-Palladium(II) Complexes in the Solid State and in Solution. In: Inorganic Chemistry. 2015 ; Vol. 54, No. 17. pp. 8436-8448.
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title = "Coordination Structure Conversion of Hydrazone-Palladium(II) Complexes in the Solid State and in Solution",
abstract = "We prepared hydrazone-palladium(II) complexes of [PdCl2(HLn)] and [PdCl(Ln)] (n = 1-3) by the reaction of [PdCl2(cod)] or [PdCl2(PhCN)2] and the hydrazone ligands of HLn {N′-(pyridin-2-ylmethylene)picolinohydrazide (HL1), N′-[1-(pyridin-2-yl)ethylidene]picolinohydrazide (HL2), and N′-[(6-methylpyridin-2-yl)methylene]picolinohydrazide (HL3)}. The structures of the complexes were determined by X-ray analysis. The hydrazone ligands had κN(py1),κN(imine) and κN(amidate),κN(py2) bidentate coordination modes in [PdCl2(HLn)] (1, n = 1; 2, n = 2) and in [PdCl2(HL3)] (3), respectively. In contrast, tridentate coordination modes of κN(py1),κN(imine),κN(py2) and κN(py1),κN(amidate),κN(py2) were observed in [PdCl(Ln)] (4, n = 1; 5, n = 2) and in [PdCl(Ln)] (6, n = 1; 7, n = 2; 8, n = 3). Thermal conversion of complexes 1-3 to complexes 6-8 proceeded in acetonitrile. Complexes 4 and 5 were obtained from complexes 1 and 2, respectively, in a basic acetonitrile solution under dark conditions. Complex 4 reverted immediately to complex 1 in an acidic acetonitrile solution that included hydrochloric acid. However, under room light, in the basic acetonitrile solution that included trimethylamine, complex 4 converted photochemically to complex 6. The thermochromic or vapochromic structure conversion of these complexes also occurred in the solid state. On heating at 180 °C, the color of the crystals of complexes 1, 2, and 3 changed from yellow to orange in the solid state. 1H NMR and/or UV-vis absorption spectroscopy confirmed that the orange complexes 6-8 were produced. The reddish-orange crystals of complexes 4 and 5 were exposed to hydrogen chloride vapor to yield the yellow products of complexes 1 and 2, respectively. (Chemical Equation Presented).",
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T1 - Coordination Structure Conversion of Hydrazone-Palladium(II) Complexes in the Solid State and in Solution

AU - Kitamura, Fumi

AU - Sawaguchi, Kana

AU - Mori, Asami

AU - Takagi, Shoji

AU - Suzuki, Takayoshi

AU - Kobayashi, Atsushi

AU - Kato, Masako

AU - Nakajima, Kiyohiko

PY - 2015/9/8

Y1 - 2015/9/8

N2 - We prepared hydrazone-palladium(II) complexes of [PdCl2(HLn)] and [PdCl(Ln)] (n = 1-3) by the reaction of [PdCl2(cod)] or [PdCl2(PhCN)2] and the hydrazone ligands of HLn {N′-(pyridin-2-ylmethylene)picolinohydrazide (HL1), N′-[1-(pyridin-2-yl)ethylidene]picolinohydrazide (HL2), and N′-[(6-methylpyridin-2-yl)methylene]picolinohydrazide (HL3)}. The structures of the complexes were determined by X-ray analysis. The hydrazone ligands had κN(py1),κN(imine) and κN(amidate),κN(py2) bidentate coordination modes in [PdCl2(HLn)] (1, n = 1; 2, n = 2) and in [PdCl2(HL3)] (3), respectively. In contrast, tridentate coordination modes of κN(py1),κN(imine),κN(py2) and κN(py1),κN(amidate),κN(py2) were observed in [PdCl(Ln)] (4, n = 1; 5, n = 2) and in [PdCl(Ln)] (6, n = 1; 7, n = 2; 8, n = 3). Thermal conversion of complexes 1-3 to complexes 6-8 proceeded in acetonitrile. Complexes 4 and 5 were obtained from complexes 1 and 2, respectively, in a basic acetonitrile solution under dark conditions. Complex 4 reverted immediately to complex 1 in an acidic acetonitrile solution that included hydrochloric acid. However, under room light, in the basic acetonitrile solution that included trimethylamine, complex 4 converted photochemically to complex 6. The thermochromic or vapochromic structure conversion of these complexes also occurred in the solid state. On heating at 180 °C, the color of the crystals of complexes 1, 2, and 3 changed from yellow to orange in the solid state. 1H NMR and/or UV-vis absorption spectroscopy confirmed that the orange complexes 6-8 were produced. The reddish-orange crystals of complexes 4 and 5 were exposed to hydrogen chloride vapor to yield the yellow products of complexes 1 and 2, respectively. (Chemical Equation Presented).

AB - We prepared hydrazone-palladium(II) complexes of [PdCl2(HLn)] and [PdCl(Ln)] (n = 1-3) by the reaction of [PdCl2(cod)] or [PdCl2(PhCN)2] and the hydrazone ligands of HLn {N′-(pyridin-2-ylmethylene)picolinohydrazide (HL1), N′-[1-(pyridin-2-yl)ethylidene]picolinohydrazide (HL2), and N′-[(6-methylpyridin-2-yl)methylene]picolinohydrazide (HL3)}. The structures of the complexes were determined by X-ray analysis. The hydrazone ligands had κN(py1),κN(imine) and κN(amidate),κN(py2) bidentate coordination modes in [PdCl2(HLn)] (1, n = 1; 2, n = 2) and in [PdCl2(HL3)] (3), respectively. In contrast, tridentate coordination modes of κN(py1),κN(imine),κN(py2) and κN(py1),κN(amidate),κN(py2) were observed in [PdCl(Ln)] (4, n = 1; 5, n = 2) and in [PdCl(Ln)] (6, n = 1; 7, n = 2; 8, n = 3). Thermal conversion of complexes 1-3 to complexes 6-8 proceeded in acetonitrile. Complexes 4 and 5 were obtained from complexes 1 and 2, respectively, in a basic acetonitrile solution under dark conditions. Complex 4 reverted immediately to complex 1 in an acidic acetonitrile solution that included hydrochloric acid. However, under room light, in the basic acetonitrile solution that included trimethylamine, complex 4 converted photochemically to complex 6. The thermochromic or vapochromic structure conversion of these complexes also occurred in the solid state. On heating at 180 °C, the color of the crystals of complexes 1, 2, and 3 changed from yellow to orange in the solid state. 1H NMR and/or UV-vis absorption spectroscopy confirmed that the orange complexes 6-8 were produced. The reddish-orange crystals of complexes 4 and 5 were exposed to hydrogen chloride vapor to yield the yellow products of complexes 1 and 2, respectively. (Chemical Equation Presented).

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