TY - JOUR
T1 - Powerful templating effect in Rb/Pd/Se(x) promoted by crown ether-like [Rb(Se8)]+ coordination. Formation of Rb2[Pd(Se4)2] · Se8
T2 - A layered Pd polyselenide with 'encapsulated' eight-membered selenium rings
AU - Wachhold, Michael
AU - Kanatzidis, Mercouri G
PY - 1999/5/5
Y1 - 1999/5/5
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 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.
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 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.
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U2 - 10.1021/ja984053g
DO - 10.1021/ja984053g
M3 - Article
AN - SCOPUS:0033526373
VL - 121
SP - 4189
EP - 4195
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 17
ER -