Name: combining solid-state and solution-based techniques: synthesis and reactivity of chalcogenidoplumbates(ii or iv)
Uploaded: 2016-12-29T15:00:00
Description: Watch this Scientific Journal Video about Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV at JoVE.com

This work was supported by the Deutsche Forschungsgemeinschaft (DFG) within the framework of SPP 1708. GT thanks the Leopoldina Nationale Akademie der Wissenschaften for a postdoctoral scholarship.

Caution: Always be cautious when working with chemicals. Apply common safety precautions, including the appropriate utilization of gloves, goggles, and a lab coat at all times. In particular, be aware that all discussed compounds containing heavy elements, as well as their elemental sources, are of high toxicity. 1,2-diaminoethane is a corrosive liquid. Alkaline metals and ternary solid-state products may react pyrophorically with air and moisture.
Note: All manipulations are performed in an a...

<ol>
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The combination of classical high-temperature, solid-state reactions with solution-based methods allows for the generation and isolation of novel compounds that cannot be synthesized by only one of these pathways. Even though, in most cases, a clear identification and full characterization of the intermediate species is difficult or essentially impossible, the general idea is straightforward and can be applied to a variety of elemental combinations. Furthermore, the actual synthetic conditions for the generation of one s...

Metal chalcogenides, such as SnSe or CuInSe, are versatile materials with a wide range of applications, for instance, as semiconductor, thermoelectric, or nonlinear optic materials1-6. Similar elemental compositions are found within chalcogenidometalates, where the metal is in a formally positive oxidation state and coordinated by negative (poly-)chalcogenide ligands to yield an overall anionic species. Different from the abovementioned materials, such metalates are additionally comprised of counter-ions, which are well separated from the anionic substructure. Typical cations are (solvated) alkali or alkaline earth metals, ammonium, or phosphonium ions. Most often, such salts with chalcogenidometalate anions have physical properties that are similar to their parental binary or ternary compounds, such as similar band gaps or photo- and semiconductivity properties. However, due to the broad range of possible anionic architectures within each elemental combination, ranging from isolated molecular species through strands and sheets of interconnected anions to extended three-dimensional frameworks, an even finer tuning of various properties can be achieved, ultimately aiming at the designed synthesis of compounds with the desired properties. Within the concept of dimensional reduction, it has been shown that a relative increase of counter ions per formula unit, which accompanies a reduction from 3D via 2D and 1D to 0D anionic architectures (0D representing molecular species), decreases the observed band gap7. Moreover, by the utilization of different (or mixtures of) chalcogenide ligands, it is even possible to achieve an ultra-fine adjustment of the band gap8,9.
Apart from these practical applications and visionary relevancies, chalcogenidometalates are still investigated for fundamental understanding, such as for the generation of novel anionic structure types or the discovery and interpretation of an unusual bonding, as well as for their unprecedented properties. Whereas the lighter congeners (i.e., oxidometalates, commonly referred to as oxometalates) have been extensively studied, in particular for potential catalytic applications, the heavier chalcogenidometalates are far less explored.
Our own interest has been focused on the synthesis, properties, and further reactivity of chalcogenidotetrelates (i.e., the heavier homologs of silicates)10,11. There is a broad variety of such compounds, ranging from water-stable and soluble binary anions, such as the [SnTe4]4- anion12; to organic, functionalized, and multinary cluster compounds, such as {[Ir3(cod)3(&#181;3-S)2](&#181;3-S)SnCl}2 (cod = cycloocta-1,5-diene)13. Our most recent studies deal with chalcogenidoplumbates, with lead as the central metal atom(s). In line with the inert-pair concept for heavy atoms, addressing the stabilization of the 6s orbital due to relativistic effects, lead is usually observed in the formal +II oxidation state. Exceptions like PbO2 are strong oxidizing agents, and the heavier lead(IV) chalcogenides, &#34;PbCh2,&#34; have not been discovered to date14. The same holds for the chalcogenidoplumbate(IV) anions, of which only [PbO4]4- has been reported15 until recently (see below).
Apart from a diverse group of structurally investigated oxidoplumbates(II,IV), there have been only few examples of chalcogenidoplumbates(II), namely [PbTe3]4-, with a trigonal pyramidal anion16; and [Pb2Ch3]2-, where Ch = Se or Te, with a trigonal bipyramidal anion17. These are synthesized by a route that has also been applied for the generation of Zintl ions18. Upon preparation of multinary intermetallic phases by fusion of the elements at high temperatures, subsequent extraction by solvents in the presence of a sequestering agent affords the desired products in (single-)crystalline form. In the case of the [Pb2Ch3]2- anions, for instance, a phase of the nominal composition &#34;KPbCh&#34; has been extracted with 1,2-diaminoethane (en) in the presence of 4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane ([2.2.2]crypt). The cryptand is necessary both for crystallization upon increase of the effective cation radius in the {K[2.2.2]crypt}+ complex counter ion, to better match the anionic size, and for a shielding of the positive charge that suppresses an electron back-donation from the anion in solution. Such salts with encapsulated cations usually reveal high tendencies for crystallization and thus, fairly good yields when compared to the corresponding salts without sequestration agents. However, a rather cumbersome synthesis or the high prices of cryptands prevent the excessive scaling of such approaches.
In contrast, K4[PbTe3]&#183;2en is synthesized via in situ reduction in solution, as has already been used as early as 1891 for the generation of the famous Pb94- anion19,20. For the latter, elemental alkaline metals were added to suspensions of lead in liquid ammonia at low temperatures, whereas for the telluridoplumbate, an alloy of the nominal composition &#34;PbTe2&#34; was reduced at room temperature, again by the addition of elemental potassium.
Our first approach towards such metalate species to be presented herein is a combination of both pathways. Here, solid-state synthesis is followed by either reduction in solution in the presence of inexpensive sequestering agents, such as 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6), or via reduction with alkaline metals that are chelated by the solvent itself, without the need for additional sequestering agents, similar to the synthesis of [Na4(en)7][Sn9]21. Our second approach also starts with high-temperature synthesis, but it is followed by solvothermal extraction of the resulting phases (i.e., extraction at elevated temperatures and pressures)22. In the following, we will present both synthetic approaches and some of our recent results upon application of these reaction pathways.

<table border="0" cellpadding="0" cellspacing="0" width="655">
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Ethan-1,2-diamine</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td style="width:136px;">E26266-2.5L</td>
			<td style="width:191px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Calcium hydride</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>213268-100G</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Tetrahydrofuran</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>401757-1L</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Sodium</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>71172-1KG</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Potassium</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>244864-50G</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Tris-triphenylphosphine rhodium chloride</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>199982-5G</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:247px;">Lead</td>
			<td style="width:81px;">Acros</td>
			<td align="right">222625000</td>
			<td></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:247px;">Selenium</td>
			<td style="width:81px;">Sigma-Aldrich</td>
			<td>209643-50G</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:247px;">18-crown-6</td>
			<td style="width:81px;">Acros</td>
			<td align="right">181561000</td>
			<td></td>
		</tr>
	</tbody>
</table>

combining solid-state and solution-based techniques: synthesis and reactivity of chalcogenidoplumbates(ii or iv)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica glass ampules). Reduction of such phases by elemental alkaline metals in amines affords crystalline chalcogenidoplumbate(II) salts comprised of [PbTe3]2- or [Pb2Ch3]2- anions, depending upon which sequestering agent for the cations is present: crown ethers, like 18-crown-6, or cryptands, like [2.2.2]crypt. Reactions of solutions of such anions with transition-metal compounds yield (poly-)chalcogenide anions or transition-metal chalcogenide clusters, including one with a &#181;-PbSe ligand (i.e., the heaviest-known CO homolog).
In contrast, the solid-state synthesis of a phase of the nominal composition &#34;K2PbSe2&#34; by successive reactions of the elements and by the subsequent solvothermal treatment in amines yields the first non-oxide/halide inorganic lead(IV) compound: a salt of the ortho-selenidoplumbate(IV) anion [PbSe4]4-. This was unexpected due to the redox potentials of Pb(IV) and Se(-II). Such methods can further be applied to other elemental combinations, leading to the formation of solutions with binary [HgTe2]2- or [BiSe3]3- anions, or to large-scale syntheses of K2Hg2Se3 or K3BiSe3 via the solid-state route.
All compounds are characterized by single-crystal X-ray diffraction and elemental analysis; solutions of plumbate salts can be investigated by 205Pb and 77Se or 127Te NMR techniques. Quantum chemical calculations using density functional theory methods enable energy comparisons. They further allow for insights into the electronic configuration and thus, the bonding situation. Molecular Rh-containing Chevrel-type compounds were found to exhibit delocalized mixed valence, whereas similar telluridopalladate anions are electron-precise; the cluster with the &#181;-PbSe ligand is energetically favored over a hypothetical CO analog, in line with the unsuccessful attempt at its synthesis. The stability of formal Pb(IV) within the [PbSe4]4- anion is mainly due to a suitable stabilization within the crystal lattice.

The existence of an ortho-selenidoplumbate anion [PbSe4]4-23 (see Figure 1, top right) has been confirmed by single crystal diffraction experiments, elemental analysis, and quantum chemical calculations. The crystal structure refinement confirms the almost-perfect tetrahedral coordination geometry, as would be expected for a lead(IV) ion, whereas DFT calculations rationalize the energetically stabilized a1...

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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV

The synthesis of chalcogenidoplumbates(II,IV) via the in situ reduction of nominal "PbCh2" (Ch = Chalcogen) and via a solid-state reaction and subsequent solvothermal reactions is presented. Additionally, reactivities of plumbate(II) solutions are portrayed, which yield the heaviest-known CO homolog known to date: the &#181;-PbSe ligand.

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)

The phases of &#34;PbCh2&#34; (Ch = Se, Te) are obtained from solid-state syntheses (i.e., by the fusion of the elements under inert conditions in silica ...

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