3 research outputs found
New High-Nuclearity Carbonyl and Carbonyl-Substituted Rhodium Clusters and Their Relationships with Polyicosahedral Carbonyl-Substituted Palladium- and Gold-Thiolates
A reinvestigation of the synthesis of [H<sub>5–<i>n</i></sub>Rh<sub>13</sub>(CO)<sub>24</sub>]<sup><i>n</i>−</sup> (<i>n</i> = 2, 3) led to isolation of a
series of Rh<sub>19</sub>, Rh<sub>26</sub>, and Rh<sub>33</sub> high-nuclearity
carbonyl
and carbonyl-substituted rhodium clusters. The [Rh<sub>19</sub>(CO)<sub>31</sub>]<sup>5–</sup> (<b>1</b>) is electronically
equivalent with [Pt<sub>19</sub>(CO)<sub>22</sub>]<sup>4–</sup>, but poor crystal diffraction data of all salts obtained to date
have prevented its geometrical analysis. The structures of Rh<sub>26</sub>(CO)<sub>29</sub>(CH<sub>3</sub>CN)<sub>11</sub> (<b>2</b>) as <b>2</b>·2CH<sub>3</sub>CN and [Rh<sub>33</sub>(CO)<sub>47</sub>]<sup>5–</sup> (<b>3</b>) as [NEt<sub>4</sub>]<sub>5</sub>[<b>3</b>]·Me<sub>2</sub>CO were determined
from complete X-ray diffraction determinations. The latter two species
adopt polyicosahedral metal frameworks, and notably, [Rh<sub>33</sub>(CO)<sub>47</sub>]<sup>5–</sup> represents the
molecular group 9 metal carbonyl cluster of highest nuclearity so
far reported
New High-Nuclearity Carbonyl and Carbonyl-Substituted Rhodium Clusters and Their Relationships with Polyicosahedral Carbonyl-Substituted Palladium- and Gold-Thiolates
A reinvestigation of the synthesis of [H<sub>5–<i>n</i></sub>Rh<sub>13</sub>(CO)<sub>24</sub>]<sup><i>n</i>−</sup> (<i>n</i> = 2, 3) led to isolation of a
series of Rh<sub>19</sub>, Rh<sub>26</sub>, and Rh<sub>33</sub> high-nuclearity
carbonyl
and carbonyl-substituted rhodium clusters. The [Rh<sub>19</sub>(CO)<sub>31</sub>]<sup>5–</sup> (<b>1</b>) is electronically
equivalent with [Pt<sub>19</sub>(CO)<sub>22</sub>]<sup>4–</sup>, but poor crystal diffraction data of all salts obtained to date
have prevented its geometrical analysis. The structures of Rh<sub>26</sub>(CO)<sub>29</sub>(CH<sub>3</sub>CN)<sub>11</sub> (<b>2</b>) as <b>2</b>·2CH<sub>3</sub>CN and [Rh<sub>33</sub>(CO)<sub>47</sub>]<sup>5–</sup> (<b>3</b>) as [NEt<sub>4</sub>]<sub>5</sub>[<b>3</b>]·Me<sub>2</sub>CO were determined
from complete X-ray diffraction determinations. The latter two species
adopt polyicosahedral metal frameworks, and notably, [Rh<sub>33</sub>(CO)<sub>47</sub>]<sup>5–</sup> represents the
molecular group 9 metal carbonyl cluster of highest nuclearity so
far reported
Interstitial Bismuth Atoms in Icosahedral Rhodium Cages: Syntheses, Characterizations, and Molecular Structures of the [Bi@Rh<sub>12</sub>(CO)<sub>27</sub>]<sup>3–</sup>, [(Bi@Rh<sub>12</sub>(CO)<sub>26</sub>)<sub>2</sub>Bi]<sup>5–</sup>, [Bi@Rh<sub>14</sub>(CO)<sub>27</sub>Bi<sub>2</sub>]<sup>3–</sup>, and [Bi@Rh<sub>17</sub>(CO)<sub>33</sub>Bi<sub>2</sub>]<sup>4–</sup> Carbonyl Clusters
The reaction of [Rh<sub>7</sub>(CO)<sub>16</sub>]<sup>3–</sup> with BiCl<sub>3</sub> under N<sub>2</sub> and at room temperature results in the formation
of the new heterometallic [Bi@Rh<sub>12</sub>(CO)<sub>27</sub>]<sup>3–</sup> cluster in high yields. Further controlled addition
of BiCl<sub>3</sub> leads first to the formation of the dimeric [(Bi@Rh<sub>12</sub>Â(CO)<sub>26</sub>)<sub>2</sub>Bi]<sup>5–</sup> and the <i>closo</i>-[Bi@Rh<sub>14</sub>Â(CO)<sub>27</sub>Bi<sub>2</sub>]<sup>3–</sup> species in low yields,
and finally, to the [Bi@Rh<sub>17</sub>Â(CO)<sub>33</sub>Bi<sub>2</sub>]<sup>4–</sup> cluster. All clusters were spectroscopically
characterized by IR and electrospray ionization mass spectrometry,
and their molecular structures were fully determined by X-ray diffraction
studies. Notably, they represent the first examples of Bi atoms interstitially
lodged in metallic cages that, in this specific case, are all based
on an icosahedral geometry. Moreover, [Bi@Rh<sub>14</sub>(CO)<sub>27</sub>Bi<sub>2</sub>]<sup>3–</sup> forms an exceptional
network of infinite zigzag chains in the solid state, thanks to intermolecular
Bi–Bi distances