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Volumn 20, Issue 12, 2001, Pages 2492-2504

Crystallographic investigation of substituted allyl and titanacyclobutane complexes of bis(2-N,N-dialkylaminoindenyl)titanium. Structure and reactivity as a function of the dialkylamino substituents

Author keywords

[No Author keywords available]

Indexed keywords

BISDIALKYLAMINOINDENYL TITANIUM; BISPENTAMETHYLCYCLOPENTADIENYL TITANIUM; BISPIPERIDINOINDENYL TITANIUM; CRYSTAL PACKING FORCES; FREE RADICAL ALKYLATION; LITHIUM CHLORIDE; ORGANIC FREE RADICALS; TITANACYCLOBUTANE COMPLEXES;

EID: 0035844898     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om000799n     Document Type: Article
Times cited : (24)

References (105)
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    • note
    • The full synthetic scope and applications of the bis(2-N,N-dimethylaminoindenyl)titanium(III) template will be detailed in a separate account.
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    • For a comment on this problem, common to certain classes of early transition metal complexes, see the supporting material in: Carney, M. J.; Walsh, P. J.; Bergman, R. G. J. Am. Chem. Soc. 1990, 112, 6426.
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    • note
    • 2 could not be determined precisely; the yield of the reaction is estimated assuming conversion to complex 5 alone, the major material isolated in this procedure. The actual yield of the reaction is lower.
  • 27
    • 0011464522 scopus 로고    scopus 로고
    • note
    • Preparation of cinnamyllithium: In a Schlenk flask, a THF solution (25 mL) of freshly distilled allyl benzene (5.0 mL. 37.7 mmol) was cooled to - 78 °C. η-Butyllithium (18.1 mL, 2.5 M in hexanes) was transferred via cannula into the flask, and the reaction mixture was left to stir for 1 h at - 78 °C. The reaction mixture was allowed to warm to room temperature and stirred for an additional hour. Removal of the solvent in vacuo yielded a yellow solid residue, which was washed repeatedly with hexane (4 × 25 mL) to give a brilliant yellow powder (3.98 g, 85%). This material was used without further characterization.
  • 29
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    • note
    • Programs for diffractometer operation, data collection, data reduction and absorption correction were those supplied by Bruker.
  • 34
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    • (b) The synthesis of 1-tributylstannyl-2-N,N-dimethylaminoindene is based on the method described by Schlosser: Desponds, O.; Schlosser, M. J. Organomet. Chem. 1991, 409, 93.
    • (1991) J. Organomet. Chem. , vol.409 , pp. 93
    • Desponds, O.1    Schlosser, M.2
  • 39
    • 0000584037 scopus 로고
    • Titanocene(III) chloride complexes typically adopt monomeric structures in the case of sterically significant ancillary ligands and chloride-bridged dimers for complexes of smaller ligands. Monomeric complexes: Pattiasina, J. W.; Heeres, H. J.; van Bolhuis, F.; Meetsma, A.; Teuben, J. H. Organometallics 1987, 6, 1004.
    • (1987) Organometallics , vol.6 , pp. 1004
    • Pattiasina, J.W.1    Heeres, H.J.2    Van Bolhuis, F.3    Meetsma, A.4    Teuben, J.H.5
  • 52
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    • and references therein
    • 3-Indenyl coordination: (a) O'Connor, J. M.; Casey, C. P. Chem. Rev. 1987, 87, 307. and references therein.
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    • O'Connor, J.M.1    Casey, C.P.2
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    • Other workers have selected different, but related parameters to quantify indenyl ligand distortions: Faller, J. W.; Crabtree, R. H.; Habib, A. Organometallics 1985, 5, 929.
    • (1985) Organometallics , vol.5 , pp. 929
    • Faller, J.W.1    Crabtree, R.H.2    Habib, A.3
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    • note
    • In several specific examples, the authors do not report HA values.
  • 83
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    • note
    • Percent pyramidalization = [360 - Σcarbon-nitrogen bonds]/[360 - 328.5] × 100.
  • 84
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    • note
    • The twist angle is the angle the lone pair on the nitrogen atom makes with the [C12-C13-C14] (or [C22-C23-C24]) plane, that is, the plane of the indenyl π-system.
  • 87
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    • note
    • 2 to regenerate the allyltitanium(III) complex, as proposed for related propargyltitanium-(III) alkylations.
  • 95
    • 0011445968 scopus 로고    scopus 로고
    • note
    • 3 in cymantrenes, ca. 1.36 Å).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.