Powerful templating effect in Rb/Pd/Se(x) promoted by crown ether-like [Rb(Se8)]+ coordination. Formation of Rb2[Pd(Se4)2] · Se8: A layered Pd polyselenide with 'encapsulated' eight-membered selenium rings

Michael Wachhold; Mercouri G. Kanatzidis

doi:10.1021/ja984053g

Powerful templating effect in Rb/Pd/Se(x) promoted by crown ether-like [Rb(Se₈)]⁺ coordination. Formation of Rb₂[Pd(Se₄)₂] · Se₈: A layered Pd polyselenide with 'encapsulated' eight-membered selenium rings

Michael Wachhold, Mercouri G. Kanatzidis

Northwestern University

Research output: Contribution to journal › Article › peer-review

20 Citations (Scopus)

Abstract

A novel layered Rb-Pd polyselenide has been synthesized by methanothermal reaction of Pd²⁺ with Se(x)^2- (from Se^2- + Se) in the presence of Rb₂CO₃. Rb₂[Pd(Se₄)₂] · Se₈ (I) reveals a unique structure with infinite [Pd(Se₄)₂]^2- sheet polyanions acting as a host for neutral Se₈ rings. The black shiny rectangular crystals of Rb₂[Pd(Se₄)₂] · Se₈ are insoluble in H₂O and common organic solvents. The compound crystallizes in the noncentrosymmetric space group P4b2 (No. 117) with a = 12.6748(8) Å, c = 6.9273(7) Å, Z = 2, and V = 1112.9(2) Å³. The [Pd(Se₄)₂]^2- sheet anion contains Pd₂₊ ions with a distorted square planar coordination geometry to four terminal Se atoms of Se₄^2- chains. The cocrystallized neutral Se₈ rings have a crown-like conformation as known from the elemental Se₈ forms. Through coordination to Rb⁺ ions they build [Rb(Se₈)⁺](n) 'cationic chains' running in the c direction. Rb₂[Pd(Se₄)₂] · Se₈ therefore differs fundamentally from its 'neighboring' alkali metal Pd polyselenides, K₂PdSe₁₀ and Cs₂PdSe₈, which each possess a three- dimensional structure with two interpenetrating [Pd(Se(x))₂]^2- frameworks. Optical spectroscopic data and the thermal stability of the compound are discussed.

Original language	English
Pages (from-to)	4189-4195
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	121
Issue number	17
DOIs	https://doi.org/10.1021/ja984053g
Publication status	Published - May 5 1999

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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Powerful templating effect in Rb/Pd/Se(x) promoted by crown ether-like [Rb(Se₈)]⁺ coordination. Formation of Rb₂[Pd(Se₄)₂] · Se₈ : A layered Pd polyselenide with 'encapsulated' eight-membered selenium rings. / Wachhold, Michael; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 121, No. 17, 05.05.1999, p. 4189-4195.

Research output: Contribution to journal › Article › peer-review

@article{78a374431f834b06ae2b49325a52cc6f,

title = "Powerful templating effect in Rb/Pd/Se(x) promoted by crown ether-like [Rb(Se8)]+ coordination. Formation of Rb2[Pd(Se4)2] · Se8: A layered Pd polyselenide with 'encapsulated' eight-membered selenium rings",

abstract = "A novel layered Rb-Pd polyselenide has been synthesized by methanothermal reaction of Pd2+ with Se(x)2- (from Se2- + Se) in the presence of Rb2CO3. Rb2[Pd(Se4)2] · Se8 (I) reveals a unique structure with infinite [Pd(Se4)2]2- sheet polyanions acting as a host for neutral Se8 rings. The black shiny rectangular crystals of Rb2[Pd(Se4)2] · Se8 are insoluble in H2O and common organic solvents. The compound crystallizes in the noncentrosymmetric space group P4b2 (No. 117) with a = 12.6748(8) {\AA}, c = 6.9273(7) {\AA}, Z = 2, and V = 1112.9(2) {\AA}3. The [Pd(Se4)2]2- sheet anion contains Pd2+ ions with a distorted square planar coordination geometry to four terminal Se atoms of Se42- chains. The cocrystallized neutral Se8 rings have a crown-like conformation as known from the elemental Se8 forms. Through coordination to Rb+ ions they build [Rb(Se8)+](n) 'cationic chains' running in the c direction. Rb2[Pd(Se4)2] · Se8 therefore differs fundamentally from its 'neighboring' alkali metal Pd polyselenides, K2PdSe10 and Cs2PdSe8, which each possess a three- dimensional structure with two interpenetrating [Pd(Se(x))2]2- frameworks. Optical spectroscopic data and the thermal stability of the compound are discussed.",

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N2 - A novel layered Rb-Pd polyselenide has been synthesized by methanothermal reaction of Pd2+ with Se(x)2- (from Se2- + Se) in the presence of Rb2CO3. Rb2[Pd(Se4)2] · Se8 (I) reveals a unique structure with infinite [Pd(Se4)2]2- sheet polyanions acting as a host for neutral Se8 rings. The black shiny rectangular crystals of Rb2[Pd(Se4)2] · Se8 are insoluble in H2O and common organic solvents. The compound crystallizes in the noncentrosymmetric space group P4b2 (No. 117) with a = 12.6748(8) Å, c = 6.9273(7) Å, Z = 2, and V = 1112.9(2) Å3. The [Pd(Se4)2]2- sheet anion contains Pd2+ ions with a distorted square planar coordination geometry to four terminal Se atoms of Se42- chains. The cocrystallized neutral Se8 rings have a crown-like conformation as known from the elemental Se8 forms. Through coordination to Rb+ ions they build [Rb(Se8)+](n) 'cationic chains' running in the c direction. Rb2[Pd(Se4)2] · Se8 therefore differs fundamentally from its 'neighboring' alkali metal Pd polyselenides, K2PdSe10 and Cs2PdSe8, which each possess a three- dimensional structure with two interpenetrating [Pd(Se(x))2]2- frameworks. Optical spectroscopic data and the thermal stability of the compound are discussed.

AB - A novel layered Rb-Pd polyselenide has been synthesized by methanothermal reaction of Pd2+ with Se(x)2- (from Se2- + Se) in the presence of Rb2CO3. Rb2[Pd(Se4)2] · Se8 (I) reveals a unique structure with infinite [Pd(Se4)2]2- sheet polyanions acting as a host for neutral Se8 rings. The black shiny rectangular crystals of Rb2[Pd(Se4)2] · Se8 are insoluble in H2O and common organic solvents. The compound crystallizes in the noncentrosymmetric space group P4b2 (No. 117) with a = 12.6748(8) Å, c = 6.9273(7) Å, Z = 2, and V = 1112.9(2) Å3. The [Pd(Se4)2]2- sheet anion contains Pd2+ ions with a distorted square planar coordination geometry to four terminal Se atoms of Se42- chains. The cocrystallized neutral Se8 rings have a crown-like conformation as known from the elemental Se8 forms. Through coordination to Rb+ ions they build [Rb(Se8)+](n) 'cationic chains' running in the c direction. Rb2[Pd(Se4)2] · Se8 therefore differs fundamentally from its 'neighboring' alkali metal Pd polyselenides, K2PdSe10 and Cs2PdSe8, which each possess a three- dimensional structure with two interpenetrating [Pd(Se(x))2]2- frameworks. Optical spectroscopic data and the thermal stability of the compound are discussed.

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