{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,16]],"date-time":"2026-02-16T15:45:41Z","timestamp":1771256741262,"version":"3.50.1"},"reference-count":95,"publisher":"Wiley","issue":"15","license":[{"start":{"date-parts":[[2003,7,28]],"date-time":"2003-07-28T00:00:00Z","timestamp":1059350400000},"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":[[2003,8,4]]},"abstract":"Abstract<\/jats:title>New mononuclear titanium and zirconium imido complexes [M(NR)(R\u20322<\/jats:sub>calix)] [M=Ti, R\u2032=Me, R=t<\/jats:italic>Bu (1<\/jats:bold>), R=2,6\u2010C6<\/jats:sub>H3<\/jats:sub>Me2<\/jats:sub> (2<\/jats:bold>), R=2,6\u2010C6<\/jats:sub>H3<\/jats:sub>i<\/jats:italic>Pr2<\/jats:sub> (3<\/jats:bold>), R=2,4,6\u2010C6<\/jats:sub>H2<\/jats:sub>Me3<\/jats:sub> (4<\/jats:bold>); M=Ti, R\u2032=Bz, R=t<\/jats:italic>Bu (5<\/jats:bold>), R=2,6\u2010C6<\/jats:sub>H3<\/jats:sub>Me2<\/jats:sub> (6<\/jats:bold>), R=2,6\u2010C6<\/jats:sub>H3<\/jats:sub>i<\/jats:italic>Pr2<\/jats:sub> (7<\/jats:bold>); M=Zr, R\u2032=Me, R=2,6\u2010C6<\/jats:sub>H3<\/jats:sub>i<\/jats:italic>Pr2<\/jats:sub> (8<\/jats:bold>)] supported by 1,3\u2010diorganyl ether p\u2010tert\u2010<\/jats:italic>butylcalix[4]arenes (R\u20322<\/jats:sub>calix) were prepared in good yield from the readily available complexes [MCl2<\/jats:sub>(Me2<\/jats:sub>calix)], [Ti(NR)Cl2<\/jats:sub>(py)3<\/jats:sub>], and [Ti(NR)Cl2<\/jats:sub>(NHMe2<\/jats:sub>)2<\/jats:sub>]. The crystallographically characterised complex [Ti(Nt<\/jats:italic>Bu)(Me2<\/jats:sub>calix)] (1<\/jats:bold>) reacts readily with CO2<\/jats:sub>, CS2<\/jats:sub>, and p<\/jats:italic>\u2010tolyl\u2010isocyanate to give the isolated complexes [Ti{N(t<\/jats:italic>Bu)C(O)O}(Me2<\/jats:sub>calix)] (10<\/jats:bold>), [{Ti(\u03bc\u2010O)(Me2<\/jats:sub>calix)}2<\/jats:sub>] (11<\/jats:bold>), [{Ti(\u03bc\u2010S)(Me2<\/jats:sub>calix)}2<\/jats:sub>] (12<\/jats:bold>), and [Ti{N(t<\/jats:italic>Bu)C(O)N(\u20104\u2010C6<\/jats:sub>H4<\/jats:sub>Me)}(Me2<\/jats:sub>calix)] (13<\/jats:bold>). In the case of CO2<\/jats:sub> and CS2<\/jats:sub>, the addition of the heterocumulene to the Ti\uf8ffN multiple bond is followed by a cycloreversion reaction to give the dinuclear complexes 11<\/jats:bold> and 12<\/jats:bold>. The X\u2010ray structure of 13\u22c54(C<\/jats:bold>7<\/jats:bold><\/jats:sub>H<\/jats:bold>8<\/jats:bold><\/jats:sub>)<\/jats:bold> clearly establishes the N,N\u2032\u2010coordination mode of the ureate ligand in this compound. Complex 1<\/jats:bold> undergoes tert<\/jats:italic>\u2010butyl\/arylamine exchange reactions to form 2, 3<\/jats:bold>, [Ti(N\u20104\u2010C6<\/jats:sub>H4<\/jats:sub>Me)(Me2<\/jats:sub>calix)] (14<\/jats:bold>), [Ti(N\u20104\u2010C6<\/jats:sub>H4<\/jats:sub>Fc)(Me2<\/jats:sub>calix)] (15<\/jats:bold>) [Fc=Fe(\u03b7<\/jats:italic>5<\/jats:sup>\u2010C5<\/jats:sub>H5<\/jats:sub>)(\u03b7<\/jats:italic>5<\/jats:sup>\u2010C5<\/jats:sub>H4<\/jats:sub>)], and [{Ti(Me2<\/jats:sub>calix)}2<\/jats:sub>{\u03bc\u2010(N\u20104\u2010C6<\/jats:sub>H4<\/jats:sub>)2<\/jats:sub>CH2<\/jats:sub>}] (16<\/jats:bold>). Reaction of 1<\/jats:bold> with H2<\/jats:sub>O, H2<\/jats:sub>S and HCl afforded the compounds [{Ti(\u03bc\u2010O)(Me2<\/jats:sub>calix)}2<\/jats:sub>] (11<\/jats:bold>), [{Ti(\u03bc\u2010S)(Me2<\/jats:sub>calix)}2<\/jats:sub>] (12<\/jats:bold>), and [TiCl2<\/jats:sub>(Me2<\/jats:sub>calix)] in excellent yields. Furthermore, treatment of 1<\/jats:bold> with two equivalents of phenols results in the formation of [Ti(O\u20104\u2010C6<\/jats:sub>H4<\/jats:sub>R)2<\/jats:sub>(Me2<\/jats:sub>calix)] (R=Me 17<\/jats:bold> or t<\/jats:italic>Bu 18<\/jats:bold>), [Ti(O\u20102,6\u2010C6<\/jats:sub>H3<\/jats:sub>Me2<\/jats:sub>)2<\/jats:sub>(Me2<\/jats:sub>calix)] (19<\/jats:bold>) and [Ti(mbmp)(Me2<\/jats:sub>calix)] (20<\/jats:bold>; H2<\/jats:sub>mbmp=2,2\u2032\u2010methylene\u2010bis(4\u2010methyl\u20106\u2010tert<\/jats:italic>\u2010butylphenol) or CH2<\/jats:sub>({CH3<\/jats:sub>}{C4<\/jats:sub>H9<\/jats:sub>}C6<\/jats:sub>H2<\/jats:sub>\u2010OH)2<\/jats:sub>). The bis(phenolate) compounds 17<\/jats:bold> and 18<\/jats:bold> with para<\/jats:italic>\u2010substituted phenolate ligands undergo elimination and\/or rearrangement reactions in the nonpolar solvents pentane or hexane. The metal\u2010containing products of the elimination reactions are dinuclear complexes [{Ti(O\u20104\u2010C6<\/jats:sub>H4<\/jats:sub>R)(Mecalix)}2<\/jats:sub>] [R=Me (23<\/jats:bold>) or t<\/jats:italic>Bu (24<\/jats:bold>)] where Mecalix=monomethyl ether of p\u2010tert\u2010<\/jats:italic>butylcalix[4]arene. The products of the rearrangement reaction are [Ti(O\u20104\u2010C6<\/jats:sub>H4<\/jats:sub>Me)2<\/jats:sub> (paco<\/jats:italic>\u2010Me2<\/jats:sub>calix)] (25<\/jats:bold>) and [Ti(O\u20104\u2010C6<\/jats:sub>H4<\/jats:sub>t<\/jats:italic>Bu)2<\/jats:sub>(paco<\/jats:italic>\u2010Me2<\/jats:sub>calix)] (26<\/jats:bold>), in which the metallated calix[4]arene ligand is coordinated in a form reminiscent of the partial cone<\/jats:italic> (paco<\/jats:italic>) conformation of calix[4]arene. In these compounds, one of the methoxy groups is located inside<\/jats:italic> the cavity of the calix[4]arene ligand. The complexes 24, 25<\/jats:bold> and 26<\/jats:bold> have been crystallographically characterised. Complexes with sterically more demanding phenolate ligands, namely 19<\/jats:bold> and 20<\/jats:bold> and the analogous zirconium complexes [Zr(O\u20104\u2010C6<\/jats:sub>H4<\/jats:sub>Me)2<\/jats:sub>(Me2<\/jats:sub>calix)] (21<\/jats:bold>) and [Zr(O\u20102,6\u2010C6<\/jats:sub>H3<\/jats:sub>Me2<\/jats:sub>)2<\/jats:sub>(Me2<\/jats:sub>calix)] (22<\/jats:bold>) do not rearrange. Density functional calculations for the model complexes [M(OC6<\/jats:sub>H5<\/jats:sub>)2<\/jats:sub>(Me2<\/jats:sub>calix)] with the calixarene possessing either cone<\/jats:italic> or partial cone<\/jats:italic> conformations are briefly presented.<\/jats:p>","DOI":"10.1002\/chem.200204656","type":"journal-article","created":{"date-parts":[[2003,7,30]],"date-time":"2003-07-30T06:15:41Z","timestamp":1059545741000},"page":"3634-3654","source":"Crossref","is-referenced-by-count":81,"title":["Synthesis and Reactivity of Calix[4]arene\u2010Supported Group 4 Imido Complexes"],"prefix":"10.1002","volume":"9","author":[{"given":"Stuart R.","family":"Dubberley","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Andreas","family":"Friedrich","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"David A.","family":"Willman","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Philip","family":"Mountford","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Udo","family":"Radius","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2003,7,28]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)80443-9"},{"key":"e_1_2_6_3_2","first-page":"161","volume-title":"Comprehensive Coordination Chemistry, Vol. 2","author":"Chisholm M. 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