Bianchini D, Barsan M M, Butler I S, Galland G B, dos Santos J H Z, Fasce D P, Williams R J J, Quijada R
McGill University, Department of Chemistry, Montréal, Québec, Canada.
Spectrochim Acta A Mol Biomol Spectrosc. 2007 Nov;68(3):956-69. doi: 10.1016/j.saa.2007.01.009. Epub 2007 Jan 19.
FT-IR photoacoustic and Raman spectroscopy have been used to study the interactions between the metallocene catalyst, Cp(2)ZrCl(2) (Cp=eta(5)-C(5)H(5)), and two polyhedral oligomeric silsesquioxanes (POSS) supports. The first silsesquioxane support, POSS(h), contains (beta-hydroxyl)-tertiary amine groups, while in the second one, POSS(u), these -OH groups have been converted into N-(p-toluyl) urethane groups. The vibrational spectra of the Cp(2)ZrCl(2):POSS(h) and Cp(2)ZrCl(2):POSS(u) samples show that the Cp(2)ZrCl(2) catalyst reacts with the C-OH groups of POSS(h) and also interacts with N-H and >CO groups of POSS(u). Furthermore, Cp(2)ZrCl(2) can react with the Si-OH groups of the POSS supports and also interact with the O atoms that are bonded to the benzene rings and the N atoms of the tertiary amines in both silsesquioxanes. As a result of the interactions between Cp(2)ZrCl(2) and the POSS supports, acidic species are generated. The Cp(2)ZrCl(2):POSS(h) mass ratio seems to be an important parameter in the formation of Zr-O bonds and the acidic species.
傅里叶变换红外光声光谱和拉曼光谱已被用于研究茂金属催化剂Cp(2)ZrCl(2)（Cp = η(5)-C(5)H(5)）与两种多面体低聚倍半硅氧烷（POSS）载体之间的相互作用。第一种倍半硅氧烷载体POSS(h)含有（β-羟基）叔胺基团，而在第二种载体POSS(u)中，这些-OH基团已转化为N-（对甲苯基）氨基甲酸酯基团。Cp(2)ZrCl(2):POSS(h)和Cp(2)ZrCl(2):POSS(u)样品的振动光谱表明，Cp(2)ZrCl(2)催化剂与POSS(h)的C-OH基团发生反应，并且还与POSS(u)的N-H和>CO基团相互作用。此外，Cp(2)ZrCl(2)可以与POSS载体的Si-OH基团发生反应，并且还与两种倍半硅氧烷中与苯环键合的O原子和叔胺的N原子相互作用。由于Cp(2)ZrCl(2)与POSS载体之间的相互作用，会生成酸性物种。Cp(2)ZrCl(2):POSS(h)的质量比似乎是形成Zr-O键和酸性物种的一个重要参数。
