Countercation Effect on CO2 Binding to Oxo Titanate with Bulky Anilide Ligands.
Countercation Effect on CO2 Binding to Oxo Titanate with Bulky Anilide Ligands.
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DOI：
10.1002/chem.201803265
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发表时间：
2018-10
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影响因子：
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通讯作者：
Albert Paparo;Jared S. Silvia;T. Spaniol;J. Okuda;C. Cummins
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文献类型：
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作者：
Albert Paparo;Jared S. Silvia;T. Spaniol;J. Okuda;C. Cummins
这项工作聚焦于在阴离子末端氧代三（苯胺基）钛配合物[(Solv)nM][OTi(N[tBu]Ar)3]m（其中M = Li、Na、K、Mg、MgMe、AlCl2、AlI2；Ar = 3,5 - Me2C6H3；Solv = Et2O、THF、12 - 冠 - 4、2,2,2 - 穴醚；n，m = 1 - 2）上二氧化碳的亲核活化。二氧化碳与[OTi(N[tBu]Ar)3]⁻（[1]⁻）的末端氧代配体的结合强度以及所生成的碳酸根部分[O2COTi(N[tBu]Ar)3]⁻（[2]⁻）的稳定性在很大程度上取决于抗衡阳离子的路易斯酸性。我们在此报道了二氧化碳结合随抗衡阳离子及抗衡阳离子配位环境的变化情况，并就阳离子路易斯酸性的下限和上限在这方面进行了讨论。提供了以锂为抗衡阳离子的氧代配合物，即[(Et2O)2Li][1]和[(12 - c - 4)Li][1]的热力学参数。
This work focuses on nucleophilic activation of CO2 at the anionic terminal oxo titanium tris(anilide) complexes [(Solv)n M][OTi(N[t Bu]Ar)3 ]m with M=Li, Na, K, Mg, MgMe, AlCl2 , AlI2 ; Ar=3,5-Me2 C6 H3 ; Solv=Et2 O, THF, 12-crown-4, 2,2,2-cryptand; n, m=1-2. The CO2 binding strength to the terminal oxo ligand of [OTi(N[t Bu]Ar)3 ]- ([1]- ) and the stability of the resulting carbonate moiety [O2 COTi(N[t Bu]Ar)3 ]- ([2]- ) are highly dependent on the Lewis acidity of the countercation. We report herein on CO2 binding as a function of countercation and countercation coordination environment, and comment in this respect on the bottom and upper limits of the cation Lewis acidity. Thermodynamic parameters are provided for oxo complexes with lithium as countercation, that is, [(Et2 O)2 Li][1] and [(12-c-4)Li][1].