| Autor: |
Kiely, A. F., Nelson, C. M., Pastor, A., Henling, L. M., Day, M. W., Bercaw, J. E. |
| Zdroj: |
Organometallics; March 30, 1998, Vol. 17 Issue: 7 p1324-1332, 9p |
| Abstrakt: |
The pentamethylcyclopentadienyl−aminoborole chloro complexes Cp*{η5-C4H4BN(CHMe2)2}MCl·LiCl (Cp* = (η5-C5Me5); M = Zr, Hf) heterolytically cleave H−X bonds to form Cp*{η5-C4H4BNH(CHMe2)2}MCl(X) (X = OR, SR, C&tbd1;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*{η5-C4H4BNH(CHMe2)2}Hf(C&tbd1;CSiMe3)2 is prepared from Cp*{η5-C4H4BN(CHMe2)2}Hf(η3-C3H5) and 2 equiv of (trimethylsilyl)acetylene. Treatment of Cp*{η5-C4H4BN(CHMe2)2}MCl·LiCl (M = Zr, Hf) with donor ligands L yields the LiCl-free complexes Cp*{η5-C4H4BN(CHMe2)2}MCl(L) (M = Zr, L = NMe2H; M = Hf, L = PMe3). Cp*{η5-C4H4BN(CHMe2)2}HfCl(PMe3) reacts with (trimethylsilyl)acetylene with loss of HN(CHMe2)2 to form Cp*{η5-C4H4B(C&tbd1;CSiMe3)}HfCl(PMe3), resulting from formal migration of acetylide from hafnium to boron. X-ray structure determinations of Cp*{η5-C4H4BNH(CHMe2)2}HfCl(C&tbd1;CSiMe3), Cp*{η5-C4H4BN(CHMe2)2}HfCl(PMe3), and Cp*{η5-C4H4B(C&tbd1;CSiMe3)}HfCl(PMe3) are reported. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
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