{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,7,30]],"date-time":"2025-07-30T10:17:10Z","timestamp":1753870630813,"version":"3.41.2"},"reference-count":66,"publisher":"Wiley","issue":"3","license":[{"start":{"date-parts":[[2021,12,27]],"date-time":"2021-12-27T00:00:00Z","timestamp":1640563200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["The Chemical Record"],"published-print":{"date-parts":[[2022,3]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The chemistry of the imido\u2010anions of the main group elements has been studied for more than three decades. The imido (NR)<jats:sup>\u2212<\/jats:sup> group is isoelectronic to the oxo (=O) group and can coordinate with metal ions through its lone pairs of electrons. The polyimido\u2010P(V) anions are well explored as they resemble the phosphorus oxo moieties such as H<jats:sub>3<\/jats:sub>PO<jats:sub>4<\/jats:sub>, H<jats:sub>2<\/jats:sub>PO<jats:sub>4<\/jats:sub><jats:sup>\u2212<\/jats:sup>, HPO<jats:sub>4<\/jats:sub><jats:sup>2\u2212<\/jats:sup> and PO<jats:sub>4<\/jats:sub><jats:sup>3\u2212<\/jats:sup> species. These imido anions are typically generated using strong main group organometallic reagents such as <jats:sup>n<\/jats:sup>BuLi, Et<jats:sub>2<\/jats:sub>Zn, Me<jats:sub>3<\/jats:sub>Al and <jats:sup>n<\/jats:sup>Bu<jats:sub>2<\/jats:sub>Mg, etc. As a result, their coordination chemistry has been restricted to reactions in anhydrous aprotic solvents for a few main group metal ions. This account presents our findings on using certain soft transition metal such Ag(I) and Pd (II) for isolating these imido\u2010P(V) anions as their corresponding self\u2010assembled clusters and cages. Using the various salts of Ag(I) ions in reaction with 2\u2010pyridyl (<jats:sup>2<\/jats:sup>Py) functionalized phosphonium salts and phosphoric triamides, we obtained the mono\u2010 and dianionic form of these imido ligands {[P(N<jats:sup>2<\/jats:sup>Py)<jats:sub>2<\/jats:sub>(NH<jats:sup>2<\/jats:sup>Py)<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup>, [P(N<jats:sup>2<\/jats:sup>Py)<jats:sub>2<\/jats:sub>(NH<jats:sup>2<\/jats:sup>Py)]<jats:sup>\u2212<\/jats:sup>, [PO(N<jats:sup>2<\/jats:sup>Py)(NH<jats:sup>2<\/jats:sup>Py)<jats:sub>2<\/jats:sub>]<jats:sup>2\u2212<\/jats:sup>} and derived interesting examples of tri, penta, hepta and octanuclear Ag(I) clusters. Interestingly, by using the salts of Pd (II) ions, the elusive imido\u2010phosphate trianions of the type [(RN)<jats:sub>3<\/jats:sub>PO]<jats:sup>3\u2212<\/jats:sup> (R=<jats:sup>t<\/jats:sup>Bu, <jats:sup>c<\/jats:sup>Hex, <jats:sup>i<\/jats:sup>Pr) were generated in a facile one pot reaction as their corresponding tri\u2010 and hexanuclear clusters of the type {Pd<jats:sub>3<\/jats:sub>[(NR)<jats:sub>3<\/jats:sub>PO](OAc)<jats:sub>3<\/jats:sub>}<jats:sub>n<\/jats:sub> (n=1 or 2). These trianions acts as a <jats:italic>cis<\/jats:italic>\u2010coordinated hexadentate ligand for a trinuclear Pd (II) cluster and serve as the polyhedral building units for constructing hitherto unknown family of neutral cages in tetrahedral {Pd<jats:sub>3<\/jats:sub>[(N<jats:sup>i<\/jats:sup>Pr)<jats:sub>3<\/jats:sub>PO]<jats:sub>4<\/jats:sub>(L)<jats:sub>6<\/jats:sub>} and cubic {Pd<jats:sub>3<\/jats:sub>[(N<jats:sup>i<\/jats:sup>Pr)<jats:sub>3<\/jats:sub>PO]<jats:sub>8<\/jats:sub>(L)<jats:sub>12<\/jats:sub>} structures in the presence of suitable linker ligands (L<jats:sup>2\u2212<\/jats:sup>). These cages show interesting host\u2010guest chemistry and post\u2010assembly reactions. Remarkably, by employing chiral tris(imido)phosphate trianions, enantiopure chiral cages of the type [(Pd<jats:sub>3<\/jats:sub>X*)<jats:sub>4<\/jats:sub>(L)<jats:sub>6<\/jats:sub>], ([X*]<jats:sup>3\u2212<\/jats:sup>=RRR\u2010 or SSS\u2010[PO(N(*CH(CH<jats:sub>3<\/jats:sub>)Ph)<jats:sub>3<\/jats:sub>]<jats:sup>3\u2212<\/jats:sup>), were synthesized and used for the chiral\u2010recognition and enantio\u2010separation of small racemic guest molecules. Some of these chiral cages were also shown to exhibit polyradical framework structures. In future, these and other similar types of cages are envisioned as potential molecular vessels for performing the reactions in their confined environment. The enantiomeric cages can be probed for asymmetric catalysis and the separation of a range of small chiral molecules.<\/jats:p>","DOI":"10.1002\/tcr.202100281","type":"journal-article","created":{"date-parts":[[2021,12,28]],"date-time":"2021-12-28T04:41:35Z","timestamp":1640666495000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Polyanionic Imido\u2010P(V) Ligands: From Transition Metal Complexes to Coordination Driven Self\u2010Assemblies"],"prefix":"10.1002","volume":"22","author":[{"given":"Meghamala","family":"Sarkar","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Science Education and Research, Pune  Dr. Homi Bhabha Road Pune 411008 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Prabhakaran","family":"Rajasekar","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Science Education and Research, Pune  Dr. Homi Bhabha Road Pune 411008 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Cavya","family":"Jose","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Science Education and Research, Pune  Dr. Homi Bhabha Road Pune 411008 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5933-4414","authenticated-orcid":false,"given":"Ramamoorthy","family":"Boomishankar","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Science Education and Research, Pune  Dr. Homi Bhabha Road Pune 411008 India"},{"name":"Centre for Energy Science Indian Institute of Science Education and Research, Pune  Dr. Homi Bhabha Road Pune 411008 India"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2021,12,27]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00029a600"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(97)90055-2"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(98)00191-X"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00029a001"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20011105)40:21<3960::AID-ANIE3960>3.0.CO;2-U"},{"key":"e_1_2_9_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20011105)113:21<4082::AID-ANGE4082>3.0.CO;2-8"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1007\/b11154"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/0010-8545(94)03002-8"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(98)00126-X"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(98)00130-1"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(02)00014-0"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(02)00012-7"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)00312-X"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990215)38:4<528::AID-ANIE528>3.0.CO;2-#"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00062a017"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic9613117"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/b004192k"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic020471h"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199706491"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1039\/b207197e"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic9011179"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2007.06.064"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1039\/b105360b"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/B400798K"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202014426"},{"key":"e_1_2_9_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202014426"},{"key":"e_1_2_9_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/om051103z"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic3014046"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/b501040c"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar970272f"},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja028485"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2006.06.058"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/cg050499e"},{"key":"e_1_2_9_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/cg101447q"},{"key":"e_1_2_9_33_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2011.01.108"},{"key":"e_1_2_9_34_1","first-page":"2691","volume":"54","author":"Marchenko A. P.","year":"1984","journal-title":"Zh. Obshch. Khim."},{"key":"e_1_2_9_35_1","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.54.2369"},{"key":"e_1_2_9_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic202373a"},{"key":"e_1_2_9_37_1","doi-asserted-by":"publisher","DOI":"10.1039\/C1DT12004B"},{"key":"e_1_2_9_38_1","doi-asserted-by":"publisher","DOI":"10.1007\/s12039-015-0818-x"},{"key":"e_1_2_9_39_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2dt30241a"},{"key":"e_1_2_9_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic400686e"},{"key":"e_1_2_9_41_1","doi-asserted-by":"publisher","DOI":"10.1002\/slct.201701770"},{"key":"e_1_2_9_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic502798r"},{"key":"e_1_2_9_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar040153h"},{"key":"e_1_2_9_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr200077m"},{"key":"e_1_2_9_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr3002824"},{"key":"e_1_2_9_46_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201905852"},{"key":"e_1_2_9_47_1","doi-asserted-by":"publisher","DOI":"10.1016\/0263-7855(93)87010-3"},{"key":"e_1_2_9_48_1","doi-asserted-by":"publisher","DOI":"10.1039\/b515612m"},{"key":"e_1_2_9_49_1","doi-asserted-by":"publisher","DOI":"10.1039\/C3CS60473J"},{"key":"e_1_2_9_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b12955"},{"key":"e_1_2_9_51_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201402553"},{"key":"e_1_2_9_52_1","doi-asserted-by":"publisher","DOI":"10.1039\/C3CS60349K"},{"key":"e_1_2_9_53_1","doi-asserted-by":"publisher","DOI":"10.1039\/cc9960001535"},{"key":"e_1_2_9_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic0112692"},{"key":"e_1_2_9_55_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201704585"},{"key":"e_1_2_9_56_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CC00207J"},{"key":"e_1_2_9_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.9b02389"},{"key":"e_1_2_9_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja212132r"},{"key":"e_1_2_9_59_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201304606"},{"key":"e_1_2_9_60_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.277.5328.936"},{"key":"e_1_2_9_61_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja016737l"},{"key":"e_1_2_9_62_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202101239"},{"key":"e_1_2_9_63_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.1c00770"},{"key":"e_1_2_9_64_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202101076"}],"container-title":["The Chemical Record"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/tcr.202100281","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/tcr.202100281","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/tcr.202100281","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,23]],"date-time":"2023-08-23T11:40:10Z","timestamp":1692790810000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/tcr.202100281"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,12,27]]},"references-count":66,"journal-issue":{"issue":"3","published-print":{"date-parts":[[2022,3]]}},"alternative-id":["10.1002\/tcr.202100281"],"URL":"https:\/\/doi.org\/10.1002\/tcr.202100281","archive":["Portico"],"relation":{},"ISSN":["1527-8999","1528-0691"],"issn-type":[{"type":"print","value":"1527-8999"},{"type":"electronic","value":"1528-0691"}],"subject":[],"published":{"date-parts":[[2021,12,27]]},"assertion":[{"value":"2021-10-27","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2021-12-27","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202100281"}}