Counterion effects in Pd polyselenides

Evolution from molecular to three-dimensional framework structures

Kang Woo Kim, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

Several palladium polyselenides were prepared by the reactions of Pd2+ ions with Se(x)2- (4 <x <6) ligands in the presence of various cations. {(CH3)N(CH2CH2)3N}2[Pd(Se6)2] (I) was prepared by the methanothermal reaction of K2PdCl4, K2Se4, and {(CH3)3N(CH2CH2)N(CH3)3}I2 in a 1:3:2 molar ratio at 110 °C. Compound I crystallizes in the space group P21/c with a = 9.403(3) Å, b = 15.050(5) Å, c = 10.807(4) Å, β = 91.73(3)°, and V = 1528.7(9) Å3. (H3NCH2CH2NH2)2[Pd(Se5)2] (II) was prepared by the methanothermal reaction of PdCl2, Na2Se4, and (H3NCH2CH2NH3)Cl2 in a 1:3:1 molar ratio at 80 °C. Compound II crystallizes in the space group P21/n with a = 9.412(3) Å, b = 8.671(3) Å, c = 12.666(3) Å, β = 98.38(2)°, and V = 1023(1) Å3. The anions in [Pd(Se5)2]2- in II and [Pd(Se6)2]2- in I are polymeric and possess layered structures. The organic cations are located between the layers. K2(H3NCH2CH2NH3)2[Pd(Se4)2·2Se4] (III) was prepared by the methanothermal reaction of PdCl2, K2Se4, and (H3NCH2CH2NH3)Cl2 in a 1:3:1 molar ratio at 80 °C. Compound III crystallizes in the space group I212121 with a = 12.587(9) Å, b = 15.271(5) Å, c = 15.404(9) Å, and V = 2961(5) Å3. The [Pd(Se4)2·2Se4]6- anion in III is composed of a [Pd(Se4)2]2- three-dimensional adamantane-like framework with large cavities that are filled with the counterions and with uncoordinated Se4 2- ligands. K6[Pd(Se5)4] (IV) was prepared by the methanothermal reaction of K2PdCl4 and K2Se5 in a 1:6 molar ratio at 80 °C. The black polyhedral crystals of IV are slightly soluble in water. Compound IV crystallizes in the space group Pbcn with a = 12.427(4) Å, b = 13.777(9) Å, c = 19.190(9) Å, and V = 3285(5) Å3. The [Pd(Se5)4]6- anion is molecular and one of the most Se-rich metal polyselenides known. It has a palladium center with four dangling Se5 2- ligands around it. Being a molecular fragment, it can be regarded as a building block for extended [Pd(Se(n))2]2- frameworks. Optical spectroscopic and thermal gravimetric analysis data for the compounds are reported.

Original languageEnglish
Pages (from-to)8124-8135
Number of pages12
JournalJournal of the American Chemical Society
Volume120
Issue number32
DOIs
Publication statusPublished - Aug 19 1998

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Molecular Evolution
Anions
Negative ions
Ligands
Palladium
Cations
Positive ions
Adamantane
Gravimetric analysis
Hot Temperature
Metals
Ions
Crystals
Water
palladium chloride
potassium palladium chloride

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Counterion effects in Pd polyselenides : Evolution from molecular to three-dimensional framework structures. / Kim, Kang Woo; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 120, No. 32, 19.08.1998, p. 8124-8135.

Research output: Contribution to journalArticle

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title = "Counterion effects in Pd polyselenides: Evolution from molecular to three-dimensional framework structures",
abstract = "Several palladium polyselenides were prepared by the reactions of Pd2+ ions with Se(x)2- (4 3)N(CH2CH2)3N}2[Pd(Se6)2] (I) was prepared by the methanothermal reaction of K2PdCl4, K2Se4, and {(CH3)3N(CH2CH2)N(CH3)3}I2 in a 1:3:2 molar ratio at 110 °C. Compound I crystallizes in the space group P21/c with a = 9.403(3) {\AA}, b = 15.050(5) {\AA}, c = 10.807(4) {\AA}, β = 91.73(3)°, and V = 1528.7(9) {\AA}3. (H3NCH2CH2NH2)2[Pd(Se5)2] (II) was prepared by the methanothermal reaction of PdCl2, Na2Se4, and (H3NCH2CH2NH3)Cl2 in a 1:3:1 molar ratio at 80 °C. Compound II crystallizes in the space group P21/n with a = 9.412(3) {\AA}, b = 8.671(3) {\AA}, c = 12.666(3) {\AA}, β = 98.38(2)°, and V = 1023(1) {\AA}3. The anions in [Pd(Se5)2]2- in II and [Pd(Se6)2]2- in I are polymeric and possess layered structures. The organic cations are located between the layers. K2(H3NCH2CH2NH3)2[Pd(Se4)2·2Se4] (III) was prepared by the methanothermal reaction of PdCl2, K2Se4, and (H3NCH2CH2NH3)Cl2 in a 1:3:1 molar ratio at 80 °C. Compound III crystallizes in the space group I212121 with a = 12.587(9) {\AA}, b = 15.271(5) {\AA}, c = 15.404(9) {\AA}, and V = 2961(5) {\AA}3. The [Pd(Se4)2·2Se4]6- anion in III is composed of a [Pd(Se4)2]2- three-dimensional adamantane-like framework with large cavities that are filled with the counterions and with uncoordinated Se4 2- ligands. K6[Pd(Se5)4] (IV) was prepared by the methanothermal reaction of K2PdCl4 and K2Se5 in a 1:6 molar ratio at 80 °C. The black polyhedral crystals of IV are slightly soluble in water. Compound IV crystallizes in the space group Pbcn with a = 12.427(4) {\AA}, b = 13.777(9) {\AA}, c = 19.190(9) {\AA}, and V = 3285(5) {\AA}3. The [Pd(Se5)4]6- anion is molecular and one of the most Se-rich metal polyselenides known. It has a palladium center with four dangling Se5 2- ligands around it. Being a molecular fragment, it can be regarded as a building block for extended [Pd(Se(n))2]2- frameworks. Optical spectroscopic and thermal gravimetric analysis data for the compounds are reported.",
author = "Kim, {Kang Woo} and Kanatzidis, {Mercouri G}",
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TY - JOUR

T1 - Counterion effects in Pd polyselenides

T2 - Evolution from molecular to three-dimensional framework structures

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N2 - Several palladium polyselenides were prepared by the reactions of Pd2+ ions with Se(x)2- (4 3)N(CH2CH2)3N}2[Pd(Se6)2] (I) was prepared by the methanothermal reaction of K2PdCl4, K2Se4, and {(CH3)3N(CH2CH2)N(CH3)3}I2 in a 1:3:2 molar ratio at 110 °C. Compound I crystallizes in the space group P21/c with a = 9.403(3) Å, b = 15.050(5) Å, c = 10.807(4) Å, β = 91.73(3)°, and V = 1528.7(9) Å3. (H3NCH2CH2NH2)2[Pd(Se5)2] (II) was prepared by the methanothermal reaction of PdCl2, Na2Se4, and (H3NCH2CH2NH3)Cl2 in a 1:3:1 molar ratio at 80 °C. Compound II crystallizes in the space group P21/n with a = 9.412(3) Å, b = 8.671(3) Å, c = 12.666(3) Å, β = 98.38(2)°, and V = 1023(1) Å3. The anions in [Pd(Se5)2]2- in II and [Pd(Se6)2]2- in I are polymeric and possess layered structures. The organic cations are located between the layers. K2(H3NCH2CH2NH3)2[Pd(Se4)2·2Se4] (III) was prepared by the methanothermal reaction of PdCl2, K2Se4, and (H3NCH2CH2NH3)Cl2 in a 1:3:1 molar ratio at 80 °C. Compound III crystallizes in the space group I212121 with a = 12.587(9) Å, b = 15.271(5) Å, c = 15.404(9) Å, and V = 2961(5) Å3. The [Pd(Se4)2·2Se4]6- anion in III is composed of a [Pd(Se4)2]2- three-dimensional adamantane-like framework with large cavities that are filled with the counterions and with uncoordinated Se4 2- ligands. K6[Pd(Se5)4] (IV) was prepared by the methanothermal reaction of K2PdCl4 and K2Se5 in a 1:6 molar ratio at 80 °C. The black polyhedral crystals of IV are slightly soluble in water. Compound IV crystallizes in the space group Pbcn with a = 12.427(4) Å, b = 13.777(9) Å, c = 19.190(9) Å, and V = 3285(5) Å3. The [Pd(Se5)4]6- anion is molecular and one of the most Se-rich metal polyselenides known. It has a palladium center with four dangling Se5 2- ligands around it. Being a molecular fragment, it can be regarded as a building block for extended [Pd(Se(n))2]2- frameworks. Optical spectroscopic and thermal gravimetric analysis data for the compounds are reported.

AB - Several palladium polyselenides were prepared by the reactions of Pd2+ ions with Se(x)2- (4 3)N(CH2CH2)3N}2[Pd(Se6)2] (I) was prepared by the methanothermal reaction of K2PdCl4, K2Se4, and {(CH3)3N(CH2CH2)N(CH3)3}I2 in a 1:3:2 molar ratio at 110 °C. Compound I crystallizes in the space group P21/c with a = 9.403(3) Å, b = 15.050(5) Å, c = 10.807(4) Å, β = 91.73(3)°, and V = 1528.7(9) Å3. (H3NCH2CH2NH2)2[Pd(Se5)2] (II) was prepared by the methanothermal reaction of PdCl2, Na2Se4, and (H3NCH2CH2NH3)Cl2 in a 1:3:1 molar ratio at 80 °C. Compound II crystallizes in the space group P21/n with a = 9.412(3) Å, b = 8.671(3) Å, c = 12.666(3) Å, β = 98.38(2)°, and V = 1023(1) Å3. The anions in [Pd(Se5)2]2- in II and [Pd(Se6)2]2- in I are polymeric and possess layered structures. The organic cations are located between the layers. K2(H3NCH2CH2NH3)2[Pd(Se4)2·2Se4] (III) was prepared by the methanothermal reaction of PdCl2, K2Se4, and (H3NCH2CH2NH3)Cl2 in a 1:3:1 molar ratio at 80 °C. Compound III crystallizes in the space group I212121 with a = 12.587(9) Å, b = 15.271(5) Å, c = 15.404(9) Å, and V = 2961(5) Å3. The [Pd(Se4)2·2Se4]6- anion in III is composed of a [Pd(Se4)2]2- three-dimensional adamantane-like framework with large cavities that are filled with the counterions and with uncoordinated Se4 2- ligands. K6[Pd(Se5)4] (IV) was prepared by the methanothermal reaction of K2PdCl4 and K2Se5 in a 1:6 molar ratio at 80 °C. The black polyhedral crystals of IV are slightly soluble in water. Compound IV crystallizes in the space group Pbcn with a = 12.427(4) Å, b = 13.777(9) Å, c = 19.190(9) Å, and V = 3285(5) Å3. The [Pd(Se5)4]6- anion is molecular and one of the most Se-rich metal polyselenides known. It has a palladium center with four dangling Se5 2- ligands around it. Being a molecular fragment, it can be regarded as a building block for extended [Pd(Se(n))2]2- frameworks. Optical spectroscopic and thermal gravimetric analysis data for the compounds are reported.

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