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Low\u2010temperature preparation of <jats:bold>2<\/jats:bold> in diethyl ether yields the Et<jats:sub>2<\/jats:sub>O adduct [Na(FPhF)(Et<jats:sub>2<\/jats:sub>O)] (<jats:bold>3<\/jats:bold>). At ambient temperature the sodium fluoride inclusion complex [Na<jats:sub>3<\/jats:sub>(FPhF)<jats:sub>3<\/jats:sub>(Et<jats:sub>2<\/jats:sub>O)(NaF)] (<jats:bold>4<\/jats:bold>) is also formed. Spectroscopic (<jats:sup>1<\/jats:sup>H, <jats:sup>13<\/jats:sup>C and <jats:sup>19<\/jats:sup>F{<jats:sup>1<\/jats:sup>H} NMR) data for <jats:bold>1<\/jats:bold>\u2013<jats:bold>5<\/jats:bold>, microanalytical analyses for compounds <jats:bold>1, 2<\/jats:bold> and <jats:bold>5<\/jats:bold> and X\u2010ray structure determinations for <jats:bold>1, 3<\/jats:bold>\u2013<jats:bold>5<\/jats:bold> confirm the formulae of these species. In the solid\u2010state, <jats:bold>1<\/jats:bold> and <jats:bold>3<\/jats:bold> possess a dimeric nature in which the formamidinate ligands coordinate through <jats:italic>\u03bc<\/jats:italic><jats:sub>2<\/jats:sub>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup> (<jats:bold>1<\/jats:bold>) and <jats:italic>\u03bc<\/jats:italic><jats:sub>2<\/jats:sub>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup> (<jats:bold>3<\/jats:bold>) binding modes. These are enabled by partial <jats:italic>ortho<\/jats:italic>\u2010fluoro donation. Compound <jats:bold>4<\/jats:bold>, which is also dimeric, contains two trisodium tris(formamidinate) units that comprise <jats:italic>\u03bc<\/jats:italic><jats:sub>2<\/jats:sub>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>\u2010FPhF ligands, a bridging diethyl ether moiety and an unprecedented <jats:italic>\u03bc<\/jats:italic><jats:sub>3<\/jats:sub>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>\u2010formamidinate donor. Together, these trinuclear units encapsulate two sodium fluoride units by <jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>\u2010<jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2010formamidinate chelation of the sodium cations (thereby creating further <jats:italic>\u03bc<\/jats:italic><jats:sub>3<\/jats:sub>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>\u2010bound formamidinates) and fluoride\u2013sodium interactions. Compound <jats:bold>5<\/jats:bold> extends the coordinative versatility of FPhF to <jats:italic>\u03bc<\/jats:italic><jats:sub>2<\/jats:sub>:<jats:italic>\u03b7<\/jats:italic><jats:sup>4<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>3<\/jats:sup> coordination by the generation of K<jats:sub>2<\/jats:sub>(<jats:italic>\u03bc<\/jats:italic><jats:sub>2<\/jats:sub>:<jats:italic>\u03b7<\/jats:italic><jats:sup>4<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>3<\/jats:sup>\u2010FPhF)<jats:sub>2<\/jats:sub> units that exhibit <jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>\u2010arene interactions. Macromolecularly, the overlaying of these units affords a polymeric solvent\u2010free structure that incites coordination of the FPhF ligands to metal atoms above and below the K<jats:sub>2<\/jats:sub>(FPhF)<jats:sub>2<\/jats:sub> plane. Overall, this generates a remarkable <jats:italic>\u03bc<\/jats:italic><jats:sub>4<\/jats:sub>:<jats:italic>\u03b7<\/jats:italic><jats:sup>4<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>3<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>2<\/jats:sup>:<jats:italic>\u03b7<\/jats:italic><jats:sup>1<\/jats:sup>\u2010amidinate binding mode that incorporates both bridging and terminal fluorine donors. Compounds <jats:bold>1<\/jats:bold>\u2013<jats:bold>5<\/jats:bold> are the first non\u2010chromium complexes of <jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2032\u2010di(<jats:italic>ortho<\/jats:italic>\u2010fluorophenyl)formamidinate.<\/jats:p>","DOI":"10.1002\/chem.200390043","type":"journal-article","created":{"date-parts":[[2003,1,17]],"date-time":"2003-01-17T11:37:15Z","timestamp":1042803435000},"page":"415-424","source":"Crossref","is-referenced-by-count":26,"title":["Structural Studies of <i>N<\/i>,<i>N<\/i>\u2032\u2010Di(<i>ortho<\/i>\u2010fluorophenyl)formamidine Group 1 Metallation"],"prefix":"10.1002","volume":"9","author":[{"given":"Marcus L.","family":"Cole","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"David J.","family":"Evans","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Peter C.","family":"Junk","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Matthew K.","family":"Smith","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2003,1,16]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(98)00202-1"},{"key":"e_1_2_6_1_3","doi-asserted-by":"publisher","DOI":"10.1016\/0010-8545(94)80059-6"},{"key":"e_1_2_6_1_4","doi-asserted-by":"publisher","DOI":"10.1016\/0010-8545(94)03012-F"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00065a014"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/0020-1693(94)03832-5"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/0020-1693(96)05180-8"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(97)05538-2"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19921040635"},{"key":"e_1_2_6_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199207371"},{"key":"e_1_2_6_7_2","unstructured":"An idealised amidinate structure possesses 120\u00b0 bond angles at each of the NCN backbone atoms namely sp2\u2010hybridised so that the nitrogen donor orbitals are directed parallel to one another. 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