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Phosphorus selenide
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<h2 id="crystallographically-confirmed-compounds">Crystallographically confirmed compounds</h2> <h3>P2Se5</h3> <p>Molecular P2Se5 has a <a href="/facts/Norbornane/IFU8eWIg">norbornane</a> like structure with two phosphorus atoms with oxidation state +3 bridged by two <a href="/facts/Diselenide/nGcl8kUK">diselenide</a> units (−Se−Se−, analogous to <a href="/facts/Disulfide/eDx5Xtlg">disulfide</a>) and one selenide unit (−Se−).<a class="footnote-ref" id="fnref:1" href="#fn:1"><sup>1</sup></a> It was isolated by solvent (<a href="/facts/Carbon_disulfide/b04Tadmy">CS2</a>) extraction from a P2Se5 amorphous phase made from the elements.<a class="footnote-ref" id="fnref:2" href="#fn:2"><sup>2</sup></a> </p> <h3>P4Se3</h3> <p>P4Se3 has been characterised crystallographically and has the same structure as the low temperature form of P4S3.<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a> It can be prepared from the elements. One preparation is to extract and recrystallise using <a href="/facts/Tetralin/0YFvrDQq">tetralin</a>. </p> <h3>P4Se5</h3> <p>The P4Se5 molecule has the same structure as <a href="/facts/Phosphorus_sulfides/W7bEcQpx">P4S5</a>.<a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> It was prepared by reacting P4Se3 with <a href="/facts/Bromine/oLfj3C7D">bromine</a> in <a href="/facts/Carbon_disulfide/b04Tadmy">CS2</a>. </p> <h3><i>catena</i>-[P4Se4]<i>x</i></h3> <p>This compound consists of polymeric chains of <a href="/facts/Norbornane/IFU8eWIg">norbornane</a>-like units joined by Se atoms.<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a> As each P atom in the repeat unit is bonded to another P atom and to two Se atoms, each P atom has a formal oxidation state of +2. </p> <h2 id="compounds-confirmed-spectroscopically">Compounds confirmed spectroscopically</h2> <h3>P4Se4</h3> <p>P4Se4 has two crystalline forms α-P4Se4 with the same molecular structure as <a href="/facts/Phosphorus_sulfides/W7bEcQpx">α-P4S4</a> and β-P4Se4 with same molecular structure as <a href="/facts/Phosphorus_sulfides/W7bEcQpx">β-P4S4</a>.<a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a> A fully characterised compound (CuI)3P4Se4 contains P4Se4 with a β-P4S4 structure.<a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a> </p> <h3>P4Se7</h3> <p>This has been reported to have the same structure as <a href="/facts/Phosphorus_sulfides/W7bEcQpx">P4S7</a>.<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a><a class="footnote-ref" id="fnref:9" href="#fn:9"><sup>9</sup></a> One well-known textbook does not mention it at all.<a class="footnote-ref" id="fnref:10" href="#fn:10"><sup>10</sup></a> </p> <h3>P4Se10</h3> <p>Molecular P4Se10 has been reported to share the same structure as <a href="/facts/Phosphorus_pentasulfide/fVlznFoE">P4S10</a> and <a href="/facts/Phosphorus_pentoxide/GKTSUNqS">P4O10</a>,<a class="footnote-ref" id="fnref:11" href="#fn:11"><sup>11</sup></a><a class="footnote-ref" id="fnref:12" href="#fn:12"><sup>12</sup></a><a class="footnote-ref" id="fnref:13" href="#fn:13"><sup>13</sup></a> but one well-known textbook does not mention it at all.<a class="footnote-ref" id="fnref:14" href="#fn:14"><sup>14</sup></a> A review (2001) examining P-Se amorphous phases did not confirm the presence of molecular P4Se10.<a class="footnote-ref" id="fnref:15" href="#fn:15"><sup>15</sup></a> The isoelectronic anion [Ge4Se10]4− which has the <a href="/facts/Adamantane/tlvgCxYf">adamantane</a> like P4O10 structure is known, an example is the sodium salt Na4[Ge4Se10].<a class="footnote-ref" id="fnref:16" href="#fn:16"><sup>16</sup></a> </p> <h2 id="other-compounds">Other compounds</h2> <p>P4Se6, P14Se, P4Se, P4Se2, P2Se, have been reported.<a class="footnote-ref" id="fnref:17" href="#fn:17"><sup>17</sup></a> </p> <h2 id="phosphorus---selenium-glasses">Phosphorus - selenium glasses</h2> <p>Phosphorus - selenium glasses have been examined using <a href="/facts/Phosphorus-31_nuclear_magnetic_resonance/0t8CaSjY">31P-NMR</a> and Raman spectroscopy. Glasses are formed in P<i>x</i>Se1−<i>x</i> over the range of compositions 0 < <i>x</i> < 0.8 with a small window around 0.52 – 0.60 centred on 0.57 (corresponding to the compound P4Se3) where there is a tendency to crystallise. For <i>x</i> < 0.47 the glasses contain Se<i>n</i> chain fragments, pyramidal P units (P <a href="/facts/Oxidation_state/W53W6s6V">oxidation state</a> +3), quasi-tetrahedral P units (P oxidation state +5, with P=Se <a href="/facts/Double_bond/qDemMn0c">double bond</a>) and P2 units (P in formal oxidation state +4). There is no evidence for an <a href="/facts/Amorphous/YTIzmrR0">amorphous</a> phase containing molecular P4Se10.<a class="footnote-ref" id="fnref:18" href="#fn:18"><sup>18</sup></a> </p> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Blachnik, R.; Lönnecke, P.; Boldt, K.; Engelen, B. (1994). "P2Se5". Acta Crystallographica Section C. 50 (5): 659–661. doi:10.1107/S0108270193010534. ISSN 0108-2701. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li> <li id="fn:2"><p>Blachnik, Roger; Lönnecke, Peter (1992). "From P4Se3I2via P3Se4I to P2Se5". Phosphorus, Sulfur, and Silicon and the Related Elements. 65 (1–4): 103–106. doi:10.1080/10426509208055329. ISSN 1042-6507. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li> <li id="fn:3"><p>Keulen, E.; Vos, A. (1959). "The crystal structure of P4Se3". Acta Crystallographica. 12 (4): 323–329. doi:10.1107/S0365110X59000950. ISSN 0365-110X. <a href="https://doi.org/10.1107%2FS0365110X59000950" target="_blank">https://doi.org/10.1107%2FS0365110X59000950</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li> <li id="fn:4"><p>Penney, G. J.; Sheldrick, G. M. (1971). "Crystal and molecular structure of tetraphosphorus pentaselenide". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 245. doi:10.1039/j19710000245. ISSN 0022-4944. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li> <li id="fn:5"><p>Ruck, Michael (1994). "Darstellung und Kristallstruktur des ersten polymeren Phosphorselenidscatena-(P4Se4)x". Zeitschrift für Anorganische und Allgemeine Chemie. 620 (10): 1832–1836. doi:10.1002/zaac.19946201028. ISSN 0044-2313. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li> <li id="fn:6"><p>Blachnik, R.; Lönnecke, P.; Nuß, J. (1994). "Neues vom P4Se4". Zeitschrift für Anorganische und Allgemeine Chemie. 620 (1): 160–166. doi:10.1002/zaac.19946200126. ISSN 0044-2313. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li> <li id="fn:7"><p>Pfitzner, A.; Reiser, Sara (1999). "(CuI)3P4Se4: β-P4Se4Cages between Columns of Copper Iodide†" (PDF). Inorganic Chemistry. 38 (10): 2451–2454. doi:10.1021/ic981042f. ISSN 0020-1669. <a href="https://epub.uni-regensburg.de/11784/1/49_%28CuI%293P4Se4%20b-P4Se4%20Cages%20between%20Columns%20of%20Copper%20Iodide.pdf" target="_blank">https://epub.uni-regensburg.de/11784/1/49_%28CuI%293P4Se4%20b-P4Se4%20Cages%20between%20Columns%20of%20Copper%20Iodide.pdf</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></p></li> <li id="fn:8"><p>Corbridge, D.E.C (2013). Phosphorus: Chemistry, Biochemistry and Technology. CRC Press, Taylor Francis Group. p. 808. ISBN 978-1-4398-4088-7. <a href="978-1-4398-4088-7" target="_blank">978-1-4398-4088-7</a> <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li> <li id="fn:9"><p>Devillanova, Francesco, ed. (2007). Handbook of Chalcogen Chemistry –New Perspectives in Sulfur, Selenium and Tellurium. Royal Society of Chemistry. ISBN 9780854043668. <a href="9780854043668" target="_blank">9780854043668</a> <a href="#fnref:9" class="footnote-back-ref">↩</a></p></li> <li id="fn:10"><p>Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, ISBN 0-12-352651-5 <a href="0-12-352651-5" target="_blank">0-12-352651-5</a> <a href="#fnref:10" class="footnote-back-ref">↩</a></p></li> <li id="fn:11"><p>Corbridge, D.E.C (2013). Phosphorus: Chemistry, Biochemistry and Technology. CRC Press, Taylor Francis Group. p. 808. ISBN 978-1-4398-4088-7. <a href="978-1-4398-4088-7" target="_blank">978-1-4398-4088-7</a> <a href="#fnref:11" class="footnote-back-ref">↩</a></p></li> <li id="fn:12"><p>Devillanova, Francesco, ed. (2007). Handbook of Chalcogen Chemistry –New Perspectives in Sulfur, Selenium and Tellurium. Royal Society of Chemistry. ISBN 9780854043668. <a href="9780854043668" target="_blank">9780854043668</a> <a href="#fnref:12" class="footnote-back-ref">↩</a></p></li> <li id="fn:13"><p>Housecroft, Catherine E; Sharpe, Alan G (2005). Inorganic Chemistry (2d ed.). Pearson education. p. 427. ISBN 978-0-13-039913-7. <a href="978-0-13-039913-7" target="_blank">978-0-13-039913-7</a> <a href="#fnref:13" class="footnote-back-ref">↩</a></p></li> <li id="fn:14"><p>Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, ISBN 0-12-352651-5 <a href="0-12-352651-5" target="_blank">0-12-352651-5</a> <a href="#fnref:14" class="footnote-back-ref">↩</a></p></li> <li id="fn:15"><p>Georgiev, D.; Mitkova, M.; Boolchand, P.; Brunklaus, G.; Eckert, H.; Micoulaut, M. (2001). "Molecular structure, glass transition temperature variation, agglomeration theory, and network connectivity of binary P-Se glasses". Physical Review B. 64 (13): 134204. Bibcode:2001PhRvB..64m4204G. doi:10.1103/PhysRevB.64.134204. ISSN 0163-1829. <a href="/wiki/Bibcode_(identifier)" target="_blank">/wiki/Bibcode_(identifier)</a> <a href="#fnref:15" class="footnote-back-ref">↩</a></p></li> <li id="fn:16"><p>Eisenmann, B.; Hansa, J. (1993). "Crystal structure of tetrasodium decaselenotetragermanate, Na4[Ge4Se10]". Zeitschrift für Kristallographie. 205 (Part-2): 325–326. Bibcode:1993ZK....205..325E. doi:10.1524/zkri.1993.205.Part-2.325. ISSN 0044-2968. <a href="/wiki/Bibcode_(identifier)" target="_blank">/wiki/Bibcode_(identifier)</a> <a href="#fnref:16" class="footnote-back-ref">↩</a></p></li> <li id="fn:17"><p>Corbridge, D.E.C (2013). Phosphorus: Chemistry, Biochemistry and Technology. CRC Press, Taylor Francis Group. p. 808. ISBN 978-1-4398-4088-7. <a href="978-1-4398-4088-7" target="_blank">978-1-4398-4088-7</a> <a href="#fnref:17" class="footnote-back-ref">↩</a></p></li> <li id="fn:18"><p>Georgiev, D.; Mitkova, M.; Boolchand, P.; Brunklaus, G.; Eckert, H.; Micoulaut, M. (2001). "Molecular structure, glass transition temperature variation, agglomeration theory, and network connectivity of binary P-Se glasses". Physical Review B. 64 (13): 134204. Bibcode:2001PhRvB..64m4204G. doi:10.1103/PhysRevB.64.134204. ISSN 0163-1829. <a href="/wiki/Bibcode_(identifier)" target="_blank">/wiki/Bibcode_(identifier)</a> <a href="#fnref:18" class="footnote-back-ref">↩</a></p></li> </ol>