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 language | English |
|---|---|
| Pages (from-to) | 8436-8448 |
| Number of pages | 13 |
| Journal | Inorganic Chemistry |
| Volume | 54 |
| Issue number | 17 |
| DOIs | |
| Publication status | Published - Sep 8 2015 |
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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 journal › Article
}
TY - JOUR
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).
UR - http://www.scopus.com/inward/record.url?scp=84941312791&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84941312791&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5b01128
DO - 10.1021/acs.inorgchem.5b01128
M3 - Article
AN - SCOPUS:84941312791
VL - 54
SP - 8436
EP - 8448
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 17
ER -