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Heterolysis of H−X Bonds by Pentamethylcyclopentadienyl−Aminoborole Complexes of Zirconium and Hafnium

Kiely, Andrew F. and Nelson, Cory M. and Pastor, Antonio and Henling, Lawrence M. and Day, Michael W. and Bercaw, John E. (1998) Heterolysis of H−X Bonds by Pentamethylcyclopentadienyl−Aminoborole Complexes of Zirconium and Hafnium. Organometallics, 17 (7). pp. 1324-1332. ISSN 0276-7333. http://resolver.caltech.edu/CaltechAUTHORS:20180518-141650830

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Abstract

The pentamethylcyclopentadienyl−aminoborole chloro complexes Cp*{η^5-C_4H_4BN(CHMe_2)_2}MCl·LiCl (Cp* = (η^5-C_5Me_5); M = Zr, Hf) heterolytically cleave H−X bonds to form Cp*{η^5-C_4H_4BNH(CHMe_2)_2}MCl(X) (X = OR, SR, C⋮CR). Control experiments using deuterium-labeled substrates show heterolysis occurs with no incorporation of deuterium into the 2,5 positions of the borole heterocycle. Cp*{η^5-C_4H_4BNH(CHMe_2)_2}Hf(C⋮CSiMe_3)_2 is prepared from Cp*{η^^5-C_4H_4BN(CHMe_2)_2}Hf(η^3-C_3H_5) and 2 equiv of (trimethylsilyl)acetylene. Treatment of Cp*{η^5-C_4H_4BN(CHMe_2)_2}MCl·LiCl (M = Zr, Hf) with donor ligands L yields the LiCl-free complexes Cp*{η^5-C_4H_4BN(CHMe_2)_2}MCl(L) (M = Zr, L = NMe2H; M = Hf, L = PMe_3). Cp*{η^5-C_4H_4BN(CHMe_2)_2}HfCl(PMe_3) reacts with (trimethylsilyl)acetylene with loss of HN(CHMe_2)_2 to form Cp*{η^5-C_4H_4B(C⋮CSiMe_3)}HfCl(PMe_3), resulting from formal migration of acetylide from hafnium to boron. X-ray structure determinations of Cp*{η^5-C_4H_4BNH(CHMe_2)_2}HfCl(C⋮CSiMe_3), Cp*{η^5-C_4H_4BN(CHMe_2)_2}HfCl(PMe_3), and Cp*{η^5-C_4H_4B(C⋮CSiMe_3)}HfCl(PMe_3) are reported.


Item Type:Article
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URLURL TypeDescription
https://dx.doi.org/10.1021/om9709345DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/om9709345PublisherSupporting Information
Additional Information:© 1998 American Chemical Society. Received October 27, 1997. This work has been supported by the National Science Foundation (Grant No. CHE-9506413). A.P. thanks the Ministerio de Educación y Ciencia of Spain for a postdoctoral fellowship. The authors wish to thank Timothy Herzog for his help in obtaining the ^2H NMR spectra and David Lynn for his help in obtaining the ^(31)P NMR spectra.
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NSFCHE-9506413
Ministerio de Educación y Ciencia (MEC)UNSPECIFIED
Record Number:CaltechAUTHORS:20180518-141650830
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180518-141650830
Official Citation:Heterolysis of H−X Bonds by Pentamethylcyclopentadienyl−Aminoborole Complexes of Zirconium and Hafnium Andrew F. Kiely, Cory M. Nelson, Antonio Pastor, Lawrence M. Henling, Michael W. Day, and John E. Bercaw Organometallics 1998 17 (7), 1324-1332 DOI: 10.1021/om9709345
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86462
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:21 May 2018 15:50
Last Modified:21 May 2018 15:50

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