{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,22]],"date-time":"2026-09-22T08:10:01Z","timestamp":1790064601484,"version":"4.0.1"},"reference-count":80,"publisher":"Wiley","issue":"13","license":[{"start":{"date-parts":[[2009,2,16]],"date-time":"2009-02-16T00:00:00Z","timestamp":1234742400000},"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":[[2009,3,16]]},"abstract":"Abstract<\/jats:title>\n \n Activating C\uf8ffF bonds<\/jats:bold>\n : Strong metal\u2013fluorocarbon coordination in complexes of electropositive metals (e.g., Na, K, Yb) with chelating polyfluorophenyl\u2010substituted amide ligands is a precursor to C\uf8ffF bond activation and fluoride abstraction when M=Yb\n II<\/jats:sup>\n , giving heteroleptic Yb\n III<\/jats:sup>\n fluoride clusters (see scheme).\n \n \n magnified image<\/jats:alt-text>\n <\/jats:graphic>\n <\/jats:boxed-text>\n <\/jats:p>\n \n Metalation of either\n N<\/jats:italic>\n ,\n N<\/jats:italic>\n \u2010diethyl\u2010 or\n N<\/jats:italic>\n ,\n N<\/jats:italic>\n \u2010dimethyl\u2010\n N<\/jats:italic>\n \u2032\u20102,3,5,6\u2010tetrafluorophenylethane\u20101,2\u2010diamines (HL\n 1\u2009a<\/jats:bold>\n ,\n 1\u2009b<\/jats:bold>\n respectively) with [M{N(SiMe\n 3<\/jats:sub>\n )\n 2<\/jats:sub>\n }] (M=Na, K) or [Yb{N(SiMe\n 3<\/jats:sub>\n )\n 2<\/jats:sub>\n }\n 2<\/jats:sub>\n (thf)\n 2<\/jats:sub>\n ] yielded the metal\u2013amido compounds [Na(L)] (\n 2\u2009a<\/jats:bold>\n ), [K(L)] (\n 3\u2009a<\/jats:bold>\n ) and [Yb(L)\n 2<\/jats:sub>\n (thf)\n 2<\/jats:sub>\n ] (\n 4\u2009a<\/jats:bold>\n ,\n 4\u2009b<\/jats:bold>\n ). The Yb complexes were also synthesised by redox transmetalation\/ligand exchange from Yb, Hg(C\n 6<\/jats:sub>\n F\n 5<\/jats:sub>\n )\n 2<\/jats:sub>\n and HL in THF or\n 4\u2009a<\/jats:bold>\n from a reaction of\n 3\u2009a<\/jats:bold>\n with YbI\n 2<\/jats:sub>\n in THF. In the presence of\n N<\/jats:italic>\n ,\n N<\/jats:italic>\n ,\n N<\/jats:italic>\n \u2032,\n N<\/jats:italic>\n \u2032\u2010 tetramethyl\u20101,2\u2010ethanediamine (TMEDA) the complexes\n 2\u2009a<\/jats:bold>\n and\n 3\u2009a<\/jats:bold>\n yielded [Na(L)\n 2<\/jats:sub>\n Na(tmeda)] (\n 5\u2009a<\/jats:bold>\n ) and [K\n 2<\/jats:sub>\n (L)\n 2<\/jats:sub>\n (tmeda)\n 2<\/jats:sub>\n ] (\n 6\u2009a<\/jats:bold>\n ), respectively, as crystalline compounds, whilst crystallisation of\n 4\u2009a<\/jats:bold>\n from DME gave [Yb(L)\n 2<\/jats:sub>\n (dme)] (\n 7\u2009a<\/jats:bold>\n ). Their structures have chelating metal\u2013amide and NR\n 2<\/jats:sub>\n donors and additional intramolecular M\u2010F\u2010C connectivity with relatively short bond lengths (Na\uf8ffF 2.65\u20133.00\u2005\u00c5; K\uf8ffF 2.70\u20133.00\u2005\u00c5; Yb\uf8ffF 2.56\u2005\u00c5). The Yb complexes undergo C\uf8ffF activation in solution forming [Yb\n 4<\/jats:sub>\n (L)\n 6<\/jats:sub>\n F\n 6<\/jats:sub>\n ] (\n 8\u2009a<\/jats:bold>\n ,\n 8\u2009b<\/jats:bold>\n ). The connectivity of [Yb\n 4<\/jats:sub>\n (L)\n 6<\/jats:sub>\n F\n 6<\/jats:sub>\n ], as shown by the X\u2010ray structures, comprised a circular Yb\n 4<\/jats:sub>\n (\u03bc\u2010F)\n 4<\/jats:sub>\n periphery with two opposing Yb centres having either one L ligand and a Yb\n 2<\/jats:sub>\n (\u03bc\u2010F)\n 2<\/jats:sub>\n bridge or two L ligands. Each polyfluorophenylamide exhibits additional intramolecular Yb\u2010F\u2010C coordination from one of the\n ortho<\/jats:italic>\n \u2010F atoms resulting in seven or eight coordinate Yb centres. An attempt to synthesise\n 4\u2009a<\/jats:bold>\n by redox transmetalation\/ligand exchange using Hg(C\uf8fdCPh)\n 2<\/jats:sub>\n as the mercury reagent gave [Yb\n 4<\/jats:sub>\n (O)\n 2<\/jats:sub>\n (L)\n 4<\/jats:sub>\n (C\uf8fdCPh)\n 4<\/jats:sub>\n (thf)\n 2<\/jats:sub>\n ]\n \u22c5<\/jats:bold>\n THF (\n 9\u2009a\u22c5<\/jats:bold>\n THF), most likely as a result of oxidation of the initially formed product.\n <\/jats:p>","DOI":"10.1002\/chem.200802294","type":"journal-article","created":{"date-parts":[[2009,2,16]],"date-time":"2009-02-16T14:44:35Z","timestamp":1234795475000},"page":"3082-3092","source":"Crossref","is-referenced-by-count":55,"title":["Intramolecular Metal\u2013Fluorocarbon Coordination, C\uf8ffF Bond Activation and Lanthanoid\u2013Fluoride Clusters with Tethered Polyfluorophenylamide Ligands"],"prefix":"10.1002","volume":"15","author":[{"given":"Glen\u2005B.","family":"Deacon","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Craig\u2005M.","family":"Forsyth","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Peter\u2005C.","family":"Junk","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jun","family":"Wang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2009,3,6]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja011472w"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/om030157a"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/om021039a"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0451012"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja800639f"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/a809275c"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00120a009"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(02)01657-1"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic062395e"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0104813"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0006908"},{"key":"e_1_2_6_12_2","unstructured":"\u00a0"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic049215q"},{"key":"e_1_2_6_14_2","first-page":"6136","volume":"120","author":"Roanelli M.","year":"2008","journal-title":"Angew. 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