Polyatomic Zintl anions of the post-transition elements

Corbett, John D.

doi:10.1021/cr00069a003

Cited by 486 publications

(303 citation statements)

References 28 publications

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“…[1][2][3][4] A large number of "ligand-free" Group 14 Zintl clusters have been prepared via the synthesis in the liquid phase or the laser vaporization in the gas phase, of which geometric and electronic structures have been explored experimentally and theoretically. [5][6][7][8][9][10][11][12][13][14][15][16][17][18] In particular, the identifications of highly symmetric cage structures of the fascinating Pb 10 2− , Sn 12 2− , and Pb 12 2− clusters [10][11][12][13] intrigue and invite investigation of the metal-doped Zintl clusters [10][11][12] in the knowledge of whether a doped atom is endohedral or exohedral.…”

Section: Introductionmentioning

confidence: 99%

Photoelectron velocity-map imaging signature of structural evolution of silver-doped lead Zintl anions

Xie

Qin

et al. 2012

The Journal of Chemical Physics

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A set of silver-doped lead Zintl anions, Ag@Pb n − (n = 5-12), have been studied using photoelectron velocity-map imaging spectroscopy and quantum chemical calculation. The structures of Ag@Pb n − (n = 7-9, 11) built upon a square pyramid base, hitherto not considered, were assigned. Overall agreement between the experimental and calculated photoelectron spectra as well as vertical detachment energies allows for structural evolution to be established. The silver atom prefers to stay outside in the n ≤ 6 clusters and intends to be encapsulated by the lead atoms in n > 6. A stable endohedral cage with bicapped square antiprism structure is formed at n = 10, the endohedral structure of which persists for the larger clusters. Especially, these Ag@Pb n − anions have been found to undergo a transition between square pyramid and pentagonal pyramid molecular structures at n = 11.

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Section: Introductionmentioning

confidence: 99%

Photoelectron velocity-map imaging signature of structural evolution of silver-doped lead Zintl anions

Xie

Qin

et al. 2012

The Journal of Chemical Physics

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“…These techniques include cathodic dissolution of electrodes composed of metal telluride alloys (15)(16)(17)(18)(19), solventothermal sealed-tube reactions (2&29), and the revisiting of the old technique of solvent extraction (30,31) of metal telluride phases (32)(33)(34)(35)(36)(37). Here we report new syntheses and characterization of the previous1 known tellurometalate anions [~d ,~e , , ]~ and [Pb2Te31L.…”

Section: Introductionmentioning

confidence: 99%

The synthesis of tellurometalates by the reduction of binary telluride melts with potassium in liquid ammonia

Park¹,

Salm²,

Ibers³

1995

Can. J. Chem.

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Abstract:The reduction of binary telluride melts with potassium in liquid ammonia in the presence of 18-Crown-6 or 2,2,2-Crypt has been employed to synthesize and precipitate tellurometalates. The method is more rapid than conventional extraction techniques and, since lower temperatures are involved, potentially unstable fragments are conserved. A melt of nominal composition CdTe, dissolved with K and 18-Crown-6 in liquid

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“…In our new structure determination we see seven ethylenediamine molecules per unit cell of a volume of 2405.5(3) Å 3 at 123 K. After obtaining identical results from crystals from different experiments, also concerning the number of solvent molecules in the structure, we propose that all studies mentioned before cover the same compound. The slightly different unit cell 6-anion can be described as a mono-capped square antiprism, the nido type with 22 skeletal electrons according to the Wade rules [3]. Deviating from perfect C 4v symmetry, the ratio of the diagonal lengths of the open square, d(Ge2-Ge4) /d(Ge1-Ge3), is 1.15, resulting in a cluster symmetry close to C 2v instead.…”

Section: Discussionmentioning

confidence: 99%

Redetermination of the crystal structure of di-(4,7,13,16,21,24-hexaoxa- 1,10-diazabicyclo[8.8.8]hexacosane-κ8N2,O6) potassium – tetrapotassium octadecagermanide – ethylenediamine (1:1:7), C25H64Ge9K3N9O6

Mayer

Giebel

Bentlohner

et al. 2015

Zeitschrift Für Kristallographie - New Crystal Structures

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C 25 H 64 Ge 9 K 3 N 9 O 6 , triclinic, P1 (no. 2), a = 9.3766 (7) Source of materialAll manipulations were carried out under argon atmosphere using a glove-box or a Schlenk line. Ethylenediamine (Alfa-Aesar, 99%) was distilled over CaH 2 and stored in a gas-tight Schlenk tube. Toluene was dried using an MBraun solvent purification system. K 12 Ge 17 was prepared from a stoichiometric mixture of the elements at 900°C in niobium ampoules. .2] (400 μmol).After six weeks many pillar-shaped, very dark red crystals of the title compound were obtained. Experimental detailsAll H atoms of cryptand and ethylenediamine molecules were included at calculated positions with HFIX and were refined using a riding model with U iso set to 1.2 U eq (C). One ethylenediamine molecule lies on a crystallographic inversion centre and shows orientational disorder. The anisotropic displacement parameters of two C and four N atoms of the solvent molecules had to be restrained using the ISOR option of the SHELX program [8]. DiscussionThe crystal structure of the title compound was previously reported two times [1,2], but both the structure determinations differ from ours. Ugrinov and Sevov postulated an amount of eight ethylenediamine molecules per unit cell, which has a volume of 2402.4 Å 3 at 100 K, but did not locate all ethylenediamine atoms on senseful positions [1]. Hauptmann and Fässler found only six solvent molecules in an even larger unit cell of 2426.8 Å 3 (150 K) [2]. In our new structure determination we see seven ethylenediamine molecules per unit cell of a volume of 2405.5(3) Å 3 at 123 K. After obtaining identical results from crystals from different experiments, also concerning the number of solvent molecules in the structure, we propose that all studies mentioned before cover the same compound. The slightly different unit cell

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Polyatomic Zintl anions of the post-transition elements

Cited by 486 publications

References 28 publications

Photoelectron velocity-map imaging signature of structural evolution of silver-doped lead Zintl anions

Photoelectron velocity-map imaging signature of structural evolution of silver-doped lead Zintl anions

The synthesis of tellurometalates by the reduction of binary telluride melts with potassium in liquid ammonia

Redetermination of the crystal structure of di-(4,7,13,16,21,24-hexaoxa- 1,10-diazabicyclo[8.8.8]hexacosane-κ8N2,O6) potassium – tetrapotassium octadecagermanide – ethylenediamine (1:1:7), C25H64Ge9K3N9O6

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