{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,2]],"date-time":"2026-05-02T04:19:14Z","timestamp":1777695554586,"version":"3.51.4"},"reference-count":101,"publisher":"Wiley","issue":"16","license":[{"start":{"date-parts":[[2007,2,13]],"date-time":"2007-02-13T00:00:00Z","timestamp":1171324800000},"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":[[2007,5,25]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Treatment of the homoleptic titanium amides [Ti(NR<jats:sub>2<\/jats:sub>)<jats:sub>4<\/jats:sub>] (R=Me or Et) with the Br\u00f8nsted acidic reagent H<jats:sub>3<\/jats:sub>N\u22c5B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> results in the elimination of one molecule of amine and the formation of the four\u2010coordinate amidoborate complexes [Ti(NR<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub>{NH<jats:sub>2<\/jats:sub>B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>}], the identity of which was confirmed by X\u2010ray crystallography. The reaction with [Zr(NMe<jats:sub>2<\/jats:sub>)<jats:sub>4<\/jats:sub>] proceeds similarly but with retention of the amine ligand to give the trigonal\u2010bipyramidal complex [Zr(NMe<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub>{NH<jats:sub>2<\/jats:sub>B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>}(NMe<jats:sub>2<\/jats:sub>H)]. Cyclopentadienyl (Cp) amidoborate complexes, [MCp(NR<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>{NH<jats:sub>2<\/jats:sub>B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>}] (M=Ti, R=Me or Et; M=Zr, R=Me) can be prepared from [MCp(NR<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub>] and H<jats:sub>3<\/jats:sub>N\u22c5B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>, and exhibit greater thermal stability than the cyclopentadienyl\u2010free compounds. H<jats:sub>3<\/jats:sub>N\u22c5B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> reacts with <jats:italic>n<\/jats:italic>BuLi or LiN(SiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub> to give LiNH<jats:sub>2<\/jats:sub>B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>, which complexes with strong Lewis acids to form ion pairs that contain weakly coordinating anions. The attempted synthesis of metallocene amidoborate complexes from dialkyl or diamide precursors and H<jats:sub>3<\/jats:sub>N\u22c5B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> was unsuccessful. However, LiNH<jats:sub>2<\/jats:sub>B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> does react with the highly electrophilic reagents [MCp<jats:sub>2<\/jats:sub>Me(\u03bc<jats:italic>\u2010<\/jats:italic>Me)B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>] to give [MCp<jats:sub>2<\/jats:sub>Me(\u03bc<jats:italic>\u2010<\/jats:italic>NH<jats:sub>2<\/jats:sub>)B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>] (M=Zr or Hf). Comparison of the molecular structures of the Group\u20054 amidoborate complexes reveals very similar B\uf8ffN, Ti\uf8ffN and Zr\uf8ffN bond lengths, which are consistent with a description of the bonding as a dative interaction between an {M(L)<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub>(NH<jats:sub>2<\/jats:sub>)} fragment and the Lewis acid B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>. Each of the structures has an intramolecular hydrogen\u2010bonding arrangement in which one of the nitrogen\u2010bonded hydrogen atoms participates in a bifurcated F\u22c5\u22c5\u22c5H\u22c5\u22c5\u22c5F interaction to <jats:italic>ortho<\/jats:italic>\u2010F atoms.<\/jats:p>","DOI":"10.1002\/chem.200601751","type":"journal-article","created":{"date-parts":[[2007,2,13]],"date-time":"2007-02-13T06:11:30Z","timestamp":1171347090000},"page":"4535-4547","source":"Crossref","is-referenced-by-count":30,"title":["The Synthesis, Structure and Reactivity of B(C<sub>6<\/sub>F<sub>5<\/sub>)<sub>3<\/sub>\u2010Stabilised Amide (M\uf8ffNH<sub>2<\/sub>) Complexes of the Group\u20054 Metals"],"prefix":"10.1002","volume":"13","author":[{"given":"Andrew\u2005J.","family":"Mountford","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"William","family":"Clegg","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Simon\u2005J.","family":"Coles","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ross\u2005W.","family":"Harrington","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Peter\u2005N.","family":"Horton","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Simon\u2005M.","family":"Humphrey","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Michael\u2005B.","family":"Hursthouse","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Joseph\u2005A.","family":"Wright","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Simon\u2005J.","family":"Lancaster","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2007,5,15]]},"reference":[{"key":"e_1_2_6_1_2","first-page":"225","author":"Bradley D. 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