Journal of the American Chemical Society

, том 130 , издание 51 , страницы 17423-17433

Alkylaluminum-Complexed Zirconocene Hydrides: Identification of Hydride-Bridged Species by NMR Spectroscopy

Тип публикации: Journal Article

Дата публикации: 2008-12-24

American Chemical Society (ACS)

Journal of the American Chemical Society

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SJR: 5.554

CiteScore: 22.5

Impact factor: 15.6

ISSN: 00027863, 15205126

DOI: 10.1021/ja8054723

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PubMed ID: 19032092

General Chemistry

Catalysis

Biochemistry

Colloid and Surface Chemistry

Краткое описание

Reactions of unbridged zirconocene dichlorides, (RnC5H5−n)2ZrCl2 (n = 0, 1, or 2), with diisobutylaluminum hydride (HAliBu2) result in the formation of tetranuclear trihydride clusters of the type (RnC5H5−n)2Zr(μ-H)3(AliBu2)3(μ-Cl)2, which contain three [AliBu2] units. Ring-bridged ansa-zirconocene dichlorides, Me2E(RnC5H4−n)2ZrCl2 with E = C or Si, on the other hand, are found to form binuclear dihydride complexes of the type Me2E(RnC5H4−n)2Zr(Cl)(μ-H)2AliBu2 with only one [AliBu2] unit. The dichotomy between unbridged and bridged zirconocene derivatives with regard to tetranuclear versus binuclear product formation is proposed to be connected to different degrees of rotational freedom of their C5-ring ligands. Alkylaluminum-complexed zirconocene dihydrides, previously observed in zirconocene-based precatalyst systems activated by methylalumoxane (MAO) upon addition of HAliBu2 or AliBu3, are proposed to be species of the type Me2Si(ind)2Zr(Me)(μ-H)2AliBu2, stabilized by interaction of their terminal Me group with a Lewis acidic site of MAO.

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Baldwin S. M. Alkylaluminum-Complexed Zirconocene Hydrides: Identification of Hydride-Bridged Species by NMR Spectroscopy // Journal of the American Chemical Society. 2008. Vol. 130. No. 51. pp. 17423-17433.

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TY - JOUR

DO - 10.1021/ja8054723

UR - https://doi.org/10.1021/ja8054723

TI - Alkylaluminum-Complexed Zirconocene Hydrides: Identification of Hydride-Bridged Species by NMR Spectroscopy

T2 - Journal of the American Chemical Society

AU - Baldwin, Steven M.

PY - 2008

DA - 2008/12/24

PB - American Chemical Society (ACS)

SP - 17423-17433

IS - 51

VL - 130

PMID - 19032092

SN - 0002-7863

SN - 1520-5126

ER -

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@article{2008_Baldwin,

author = {Steven M. Baldwin},

title = {Alkylaluminum-Complexed Zirconocene Hydrides: Identification of Hydride-Bridged Species by NMR Spectroscopy},

journal = {Journal of the American Chemical Society},

year = {2008},

volume = {130},

publisher = {American Chemical Society (ACS)},

month = {dec},

url = {https://doi.org/10.1021/ja8054723},

number = {51},

pages = {17423--17433},

doi = {10.1021/ja8054723}

}

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Baldwin, Steven M., et al. “Alkylaluminum-Complexed Zirconocene Hydrides: Identification of Hydride-Bridged Species by NMR Spectroscopy.” Journal of the American Chemical Society, vol. 130, no. 51, Dec. 2008, pp. 17423-17433. https://doi.org/10.1021/ja8054723.