{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,6]],"date-time":"2026-03-06T17:52:52Z","timestamp":1772819572489,"version":"3.50.1"},"reference-count":98,"publisher":"Wiley","issue":"48","license":[{"start":{"date-parts":[[2009,11,9]],"date-time":"2009-11-09T00:00:00Z","timestamp":1257724800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2009,12,14]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A cyclotriphosphazene bearing two 4\u2010oxypyridine groups on the same phosphorus atom, <jats:italic>gem<\/jats:italic>\u2010[N<jats:sub>3<\/jats:sub>P<jats:sub>3<\/jats:sub>(O<jats:sub>2<\/jats:sub>C<jats:sub>12<\/jats:sub>H<jats:sub>8<\/jats:sub>)<jats:sub>2<\/jats:sub>(OC<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>N\u20104)<jats:sub>2<\/jats:sub>] (<jats:bold>I<\/jats:bold>), and its analogous polymer [{NP(O<jats:sub>2<\/jats:sub>C<jats:sub>12<\/jats:sub>H<jats:sub>8<\/jats:sub>)}<jats:sub>0.7<\/jats:sub>{NP(OC<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>N\u20104)<jats:sub>2<\/jats:sub>}<jats:sub>0.3<\/jats:sub>]<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub> (<jats:bold>II<\/jats:bold>), have been used to prepare gold or silver, cyclic and polymeric, metallophosphazenes. The following complexes, <jats:italic>gem<\/jats:italic>\u2010[N<jats:sub>3<\/jats:sub>P<jats:sub>3<\/jats:sub>(O<jats:sub>2<\/jats:sub>C<jats:sub>12<\/jats:sub>H<jats:sub>8<\/jats:sub>)<jats:sub>2<\/jats:sub>(OC<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>N\u20104{ML})<jats:sub>2<\/jats:sub>] (ML=Au(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>) (<jats:bold>1<\/jats:bold>) or Au(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> (<jats:bold>2<\/jats:bold>)), [N<jats:sub>3<\/jats:sub>P<jats:sub>3<\/jats:sub>(O<jats:sub>2<\/jats:sub>C<jats:sub>12<\/jats:sub>H<jats:sub>8<\/jats:sub>)<jats:sub>2<\/jats:sub>(OC<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>N\u20104{AuPPh<jats:sub>3<\/jats:sub>})<jats:sub>2<\/jats:sub>][NO<jats:sub>3<\/jats:sub>]<jats:sub>2<\/jats:sub> (<jats:bold>3<\/jats:bold>), and [N<jats:sub>3<\/jats:sub>P<jats:sub>3<\/jats:sub>(O<jats:sub>2<\/jats:sub>C<jats:sub>12<\/jats:sub>H<jats:sub>8<\/jats:sub>)<jats:sub>2<\/jats:sub>(OC<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>N\u20104{AgPPh<jats:sub>2<\/jats:sub>R})<jats:sub>2<\/jats:sub>][SO<jats:sub>3<\/jats:sub>CF<jats:sub>3<\/jats:sub>]<jats:sub>2<\/jats:sub> (R=Ph (<jats:bold>4<\/jats:bold>) or Me (<jats:bold>5<\/jats:bold>)) have been obtained. Complexes <jats:bold>1<\/jats:bold> and <jats:bold>4<\/jats:bold> are excellent models for the preparation of the analogous polymers [{NP(O<jats:sub>2<\/jats:sub>C<jats:sub>12<\/jats:sub>H<jats:sub>8<\/jats:sub>)}<jats:sub>0.7<\/jats:sub>{NP(OC<jats:sub>5<\/jats:sub>H<jats:sub>4<\/jats:sub>N\u20104{ML})<jats:sub>2<\/jats:sub>}<jats:sub>0.3<\/jats:sub>]<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub> (ML=Au(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>) (<jats:bold>P1<\/jats:bold>), Ag(OSO<jats:sub>2<\/jats:sub>CF<jats:sub>3<\/jats:sub>)PPh<jats:sub>3<\/jats:sub> (<jats:bold>P2<\/jats:bold>)). All complexes have been characterized by elemental analysis, various spectroscopic methods, and mass spectrometry. The polymers were further investigated by thermochemical methods (thermogravimetric analysis) and differential scanning calorimetry. For compounds <jats:bold>1<\/jats:bold>\u2013<jats:bold>5<\/jats:bold> and for the starting phosphazene <jats:bold>I<\/jats:bold>, a mixture of different stereoisomers may be expected. The stereochemistry in solution has been studied by variable\u2010temperature NMR spectroscopy studies, which provided evidence for interconversion processes that involve changes in the chirality of a 2,2\u2032\u2010dioxybiphenyl group. A single\u2010crystal X\u2010ray analysis of the gold complex <jats:bold>2<\/jats:bold> confirmed not only the proposed structure, but also <jats:italic>S,S<\/jats:italic> and <jats:italic>R,R<\/jats:italic> configurations at the two biphenoxy\u2010substituted phosphorus centers, in contrast to those observed for the precursor <jats:bold>I<\/jats:bold>. Pyrolysis of these new metallophosphazenes was also studied. Notably, pyrolysis of the gold derivatives gave macroporous metallic gold sponges without the requirement of either an external reducing agent or a porous support. These materials were all characterized by XRD, TEM, SEM, and energy\u2010dispersive X\u2010ray spectroscopy.<\/jats:p>","DOI":"10.1002\/chem.200902180","type":"journal-article","created":{"date-parts":[[2009,11,10]],"date-time":"2009-11-10T09:59:45Z","timestamp":1257847185000},"page":"13509-13520","source":"Crossref","is-referenced-by-count":23,"title":["Metallocyclo\u2010 and Polyphosphazenes Containing Gold or Silver: Thermolytic Transformation into Nanostructured Materials"],"prefix":"10.1002","volume":"15","author":[{"given":"Josefina","family":"Jim\u00e9nez","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Antonio","family":"Laguna","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mohamed","family":"Benouazzane","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jose Antonio","family":"Sanz","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Carlos","family":"D\u00edaz","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mar\u00eda\u2005Luisa","family":"Valenzuela","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Peter\u2005G.","family":"Jones","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2009,12,8]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","first-page":"61","volume-title":"Inorganic Polymers","author":"Mark J. 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The diffraction peaks at 20.93 29.78 33.37 36.69 47.94 52.81 55.14 and 57.43\u00b0 (marked as full circles) correspond to Ag3PO4(JCPDS card no. 70\u20130702) and those at 2\u03b8=6.43 17.04 and 18.81\u00b0 (marked as squares) can be assigned to P4O7 which has also been observed in the residue resulting from the pyrolysis of other organometallic phosphazenes.[17]"},{"key":"e_1_2_6_95_2","unstructured":"EDAX analyses show an increase in the Ag content and a decrease in the P content going from the plane void (Ag3PO4) to the grain (Ag). Figure\u20059\u2009f shows the presence of only Ag in the grains and Figure\u20059\u2009g indicates the presence of Ag P and O at a void point."},{"key":"e_1_2_6_96_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767307043930"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200902180","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200902180","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T17:33:56Z","timestamp":1760290436000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200902180"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,12,8]]},"references-count":98,"journal-issue":{"issue":"48","published-print":{"date-parts":[[2009,12,14]]}},"alternative-id":["10.1002\/chem.200902180"],"URL":"https:\/\/doi.org\/10.1002\/chem.200902180","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,12,8]]}}}