Tetrakis(dimethyltin)-Containing Tungstophosphate
[{Sn(CH<sub>3</sub>)<sub>2</sub>}<sub>4</sub>(H<sub>2</sub>P<sub>4</sub>W<sub>24</sub>O<sub>92</sub>)<sub>2</sub>]<sup>28-</sup>: First Evidence for a Lacunary Preyssler
Ion
Firasat Hussain
Ulrich Kortz
Bineta Keita
Louis Nadjo
Michael T. Pope
10.1021/ic051990y.s001
https://acs.figshare.com/articles/dataset/Tetrakis_dimethyltin_Containing_Tungstophosphate_Sn_CH_sub_3_sub_sub_2_sub_sub_4_sub_H_sub_2_sub_P_sub_4_sub_W_sub_24_sub_O_sub_92_sub_sub_2_sub_sup_28_sup_First_Evidence_for_a_Lacunary_Preyssler_Ion/3242566
We demonstrate for the first time that the superlacunary polyanion [H<sub>2</sub>P<sub>4</sub>W<sub>24</sub>O<sub>94</sub>]<sup>22-</sup> reacts with electrophiles. One-pot reaction of this precursor polyanion with dimethyltin dichloride in aqueous acidic medium results in the hybrid
organic−inorganic [{Sn(CH<sub>3</sub>)<sub>2</sub>}<sub>4</sub>(H<sub>2</sub>P<sub>4</sub>W<sub>24</sub>O<sub>92</sub>)<sub>2</sub>]<sup>28-</sup> (<b>1</b>). Single-crystal X-ray analysis was carried out on K<sub>17</sub>Li<sub>11</sub>[{Sn(CH<sub>3</sub>)<sub>2</sub>}<sub>4</sub>(H<sub>2</sub>P<sub>4</sub>W<sub>24</sub>O<sub>92</sub>)<sub>2</sub>]·51H<sub>2</sub>O (<b>1a</b>), which crystallizes in the tetragonal system, space group <i>P</i>4<sub>2</sub>/<i>nmc</i>, <i>a</i> = <i>b</i> =
21.5112(17) and <i>c</i> = 27.171(3) Å, and <i>Z</i> = 2. Polyanion <b>1</b> is composed of two (P<sub>4</sub>W<sub>24</sub>O<sub>92</sub>) fragments that are
linked by four equivalent diorganotin groups. The unprecedented assembly <b>1</b> has <i>D</i><sub>2</sub><i><sub>d</sub></i> symmetry and contains a
hydrophobic pocket in the center of the molecule. The cyclic voltammetry pattern of <b>1</b> is constituted by a first
broad, 16-electron reduction wave followed by a second large current intensity wave. No splitting of the first reduction
wave could be obtained at moderate scan rate values, even though two well-separated oxidation processes are
associated with it. The characteristics of the first wave are clearly different from those obtained for the polyanion
precursor [H<sub>2</sub>P<sub>4</sub>W<sub>24</sub>O<sub>94</sub>]<sup>22-</sup> and the related, wheel-shaped [H<sub>7</sub>P<sub>8</sub>W<sub>48</sub>O<sub>184</sub>]<sup>33-</sup>, which is due to the {Sn(CH<sub>3</sub>)<sub>2</sub>} fragments
in <b>1</b>. However, no feature was observed in the voltammogram which could be associated with reduction of the Sn
centers.
2006-01-23 00:00:00
Lacunary Preyssler Ion
intensity wave
scan rate values
fragment
equivalent diorganotin groups
dimethyltin dichloride
First Evidence
acidic medium results
D 2
polyanion precursor
P 4 W 24 O 92
2. Polyanion 1
cyclic voltammetry pattern
H 7 P 8 W 48 O 184
superlacunary polyanion
reduction wave
assembly 1
H 2 P 4 W 24 O 92
H 2 P 4 W 24 O 94
precursor polyanion
Sn centers