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We thus complete the series of crown ether coordinated alkali metal diphenyl phosphides and reveal that the structural diversity increases upon descending the group. Including the previously reported Na and K derivatives, we performed a detailed study of the title compounds in solution that strongly indicated all of them are monomers with an alkali metal phosphide AM\u2013P interaction. We further investigated the influence of the phosphorus\u2010bound substituents on the bond between the Cs(18\u2010crown\u20106) and the phosphide fragment. For this purpose, we synthesized and characterized two new cesium phosphides, alkyl\u2010aryl Cs(18\u2010crown\u20106)P<jats:italic><jats:sup>t<\/jats:sup><\/jats:italic>BuPh (<jats:bold>4<jats:sup>Cs<\/jats:sup><\/jats:bold>) and bis\u2010alkyl Cs(18\u2010crown\u20106)P<jats:italic><jats:sup>t<\/jats:sup><\/jats:italic>Bu<jats:sub>2<\/jats:sub> (<jats:bold>5<jats:sup>Cs<\/jats:sup><\/jats:bold>). We observed here that the heavy alkali metals Rb and Cs favor coordination via <jats:italic>\u03c0\u2010<\/jats:italic>arene interactions\u00a0over the P donor dative interactions. Finally, we used state\u2010of\u2010the\u2010art quantum chemical methods to analyze the bonding situation in the title series of compounds.<\/jats:p>","DOI":"10.1002\/chem.202502127","type":"journal-article","created":{"date-parts":[[2025,8,4]],"date-time":"2025-08-04T04:30:15Z","timestamp":1754281815000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Crown Ether Supported Alkali Metal Phosphides: Synthesis, Structures and Bonding"],"prefix":"10.1002","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2378-8406","authenticated-orcid":false,"given":"Felix","family":"Kr\u00e4mer","sequence":"first","affiliation":[{"name":"Department of Pure and Applied Chemistry University of Strathclyde  Glasgow G1 1XL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Michelle H.","family":"Crabbe","sequence":"additional","affiliation":[{"name":"Department of Pure and Applied Chemistry University of Strathclyde  Glasgow G1 1XL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3652-6015","authenticated-orcid":false,"given":"Alan R.","family":"Kennedy","sequence":"additional","affiliation":[{"name":"Department of Pure and Applied Chemistry University of Strathclyde  Glasgow G1 1XL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5643-9256","authenticated-orcid":false,"given":"Catherine E.","family":"Weetman","sequence":"additional","affiliation":[{"name":"Department of Pure and Applied Chemistry University of Strathclyde  Glasgow G1 1XL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0186-9774","authenticated-orcid":false,"given":"Israel","family":"Fern\u00e1ndez","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Org\u00e1nica I Facultad de Ciencias Qu\u00edmicas and Centro de Innovaci\u00f3n en Qu\u00edmica Avanzada (ORFEO\u2010CINQA) Universidad Complutense de Madrid  Madrid 28040 Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1015-2564","authenticated-orcid":false,"given":"Robert E.","family":"Mulvey","sequence":"additional","affiliation":[{"name":"Department of Pure and Applied Chemistry University of Strathclyde  Glasgow G1 1XL UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,8,3]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1098\/rspl.1857.0084"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19170500142"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202010963"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00047"},{"key":"e_1_2_8_3_3","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-019-0250-6"},{"key":"e_1_2_8_3_4","doi-asserted-by":"publisher","DOI":"10.1016\/B0-08-045047-4\/00034-0"},{"key":"e_1_2_8_3_5","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-3055(08)60672-3"},{"key":"e_1_2_8_3_6","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199315013"},{"key":"e_1_2_8_3_7","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)70125-0"},{"key":"e_1_2_8_3_8","first-page":"1","volume-title":"Encyclopedia of Inorganic and Bioinorganic Chemistry","author":"Harvey M. 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