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Article: Half-Sandwich Titanium(IV) Complexes with Klaui's Tripod Ligand

TitleHalf-Sandwich Titanium(IV) Complexes with Klaui's Tripod Ligand
Authors
Issue Date2003
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2003, v. 42 n. 6, p. 1842-1847 How to Cite?
AbstractTreatment of [Ti(O-i-Pr)2Cl2] with NaLOEt (LOEt- = [CpCo{P(O)(OEt)2}3]-, Cp = η5-C5H5) afforded [LOEtTi(O-i-Pr)2Cl] that reacted with HCl in ether to give [LOEtTiCl3] (1). The average Ti−O and Ti−Cl distances in 1 are 1.975 and 2.293 Å, respectively. Reaction of titanyl sulfate with NaLOEt in water followed by addition of HBF4 afforded [LOEtTiF3] (2), the Ti−O and Ti−F distances of which are 2.020(2) and 1.792(2) Å, respectively. The Zr(IV) analogue [LOEtZrF3] (3) was prepared similarly from zirconyl nitrate, NaLOet, and HBF4 in water. The Zr−O and average Zr−F distances in 3 are 2.139(2) and 1.938(2) Å, respectively. Treatment of 1 with tetrachlorocatechol (H2Cl4cat) afforded [LOEtTi(Cl4cat)Cl] (4). The average Ti−O(P), Ti−O(C), and Ti−Cl distances in 4 are 1.972, 1.926, and 2.334 Å, respectively. Hydrolysis of 4 in the presence of Et3N yielded the μ-oxo dimer [(LOEt)2Ti2(Cl4cat)2(μ-O)] (5). The average Ti−O(P), Ti−O(C), and Ti−O(Ti) distances in 5 are 2.027, 1.926, and 1.7977(9) Å. Treatment of 1 with 1,1‘-binaphthol (BINOLH2) in the presence of Et3N afforded [(LOEt)2Ti2(μ-O)2(μ-BINOL)]·2BINOLH2 (6·2BINOLH2). Complex 1 is capable of catalyzing ring opening of epoxides with Me3SiN3 under solvent-free conditions presumably via a Ti−azide intermediate.
Persistent Identifierhttp://hdl.handle.net/10722/69692
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorLam, TCHen_HK
dc.contributor.authorChan, EYYen_HK
dc.contributor.authorMak, WLen_HK
dc.contributor.authorLo, SMFen_HK
dc.contributor.authorWilliams, IDen_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorLeung, WHen_HK
dc.date.accessioned2010-09-06T06:15:59Z-
dc.date.available2010-09-06T06:15:59Z-
dc.date.issued2003en_HK
dc.identifier.citationInorganic Chemistry, 2003, v. 42 n. 6, p. 1842-1847en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69692-
dc.description.abstractTreatment of [Ti(O-i-Pr)2Cl2] with NaLOEt (LOEt- = [CpCo{P(O)(OEt)2}3]-, Cp = η5-C5H5) afforded [LOEtTi(O-i-Pr)2Cl] that reacted with HCl in ether to give [LOEtTiCl3] (1). The average Ti−O and Ti−Cl distances in 1 are 1.975 and 2.293 Å, respectively. Reaction of titanyl sulfate with NaLOEt in water followed by addition of HBF4 afforded [LOEtTiF3] (2), the Ti−O and Ti−F distances of which are 2.020(2) and 1.792(2) Å, respectively. The Zr(IV) analogue [LOEtZrF3] (3) was prepared similarly from zirconyl nitrate, NaLOet, and HBF4 in water. The Zr−O and average Zr−F distances in 3 are 2.139(2) and 1.938(2) Å, respectively. Treatment of 1 with tetrachlorocatechol (H2Cl4cat) afforded [LOEtTi(Cl4cat)Cl] (4). The average Ti−O(P), Ti−O(C), and Ti−Cl distances in 4 are 1.972, 1.926, and 2.334 Å, respectively. Hydrolysis of 4 in the presence of Et3N yielded the μ-oxo dimer [(LOEt)2Ti2(Cl4cat)2(μ-O)] (5). The average Ti−O(P), Ti−O(C), and Ti−O(Ti) distances in 5 are 2.027, 1.926, and 1.7977(9) Å. Treatment of 1 with 1,1‘-binaphthol (BINOLH2) in the presence of Et3N afforded [(LOEt)2Ti2(μ-O)2(μ-BINOL)]·2BINOLH2 (6·2BINOLH2). Complex 1 is capable of catalyzing ring opening of epoxides with Me3SiN3 under solvent-free conditions presumably via a Ti−azide intermediate.-
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleHalf-Sandwich Titanium(IV) Complexes with Klaui's Tripod Liganden_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=42&issue=6&spage=1842&epage=1847&date=2003&atitle=Half-sandwich+titanium(IV)+complexes+with+Kle4ui%27s+tripod+liganden_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1021/ic020287w-
dc.identifier.pmid12639116-
dc.identifier.hkuros76340en_HK
dc.identifier.isiWOS:000181676500009-

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