Syntheses, structures, and properties of phenyltrihydroborate complexes of zirconocene and titanocene
Resource
Journal of Organometallic Chemistry 690 (2): 291-300
Journal
Journal of Organometallic Chemistry
Journal Volume
690
Journal Issue
2
Pages
291-300
Date Issued
2005
Author(s)
Abstract
The phenyltrihydroborate complexes, Cp 2ZrCl{(μ-H) 2BHPh}, 1, and Cp 2Zr{(μ-H) 2BHPh} 2 • (1/2 toluene), 2, were prepared from the reactions of Cp 2ZrCl 2 with one and two moles of LiBH 3Ph. The Zr-H-B bonds in 2 are stable under vacuum at 100°C for hours without significant decomposition. An inductive effect has been proposed for this strong interaction. This hydrogen bridge bond can be broken upon reacting with the Lewis base N(C 2H 5) 3 to produce (C 2H 5) 3N • BH 2Ph and the zirconium hydride compound Cp 2ZrH{(μ-H) 2BHPh}, 3. Compound 3 also can be prepared from the reaction of Cp 2ZrHCl with LiBH 3Ph. The reaction of 1 with the Lewis acid B(C 6F 5) 3 is solvent dependent, the metathesis product Cp 2ZrCl{(μ-H) 2B(C 6F 5) 2}, 4, was formed in the toluene solution, whereas the ionic complex [Cp 2ZrCl(OEt 2)][HB(C 6F 5) 3], 5, was isolated from the ether solution. The reaction of titanocene dichloride, Cp 2TiCl 2, with LiBH 3Ph produced a 17-electron, paramagnetic complex, Cp 2Ti{(μ-H) 2BHPh}, 6. Single crystal X-ray structures of 1, 2, 3, 4, 5, and 6 were also determined. A coplanar structure of the four bridge hydrogens in 2 was observed. © 2004 Elsevier B.V. All rights reserved.
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