- Homoleptic Perchlorophenyl "ate" Complexes of Thorium(IV) and Uranium(IV)
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The reaction of AnCl4(DME)n (An = Th, n = 2; U, n = 0) with 5 equiv of LiC6Cl5 in Et2O resulted in the formation of homoleptic actinide-aryl "ate"complexes [Li(DME)2(Et2O)]2[Li(DME)2][Th(C6Cl5)5]3 ([Li][1]) and [Li(Et2O)4][U(C6Cl5)5] ([Li][2]). Similarly, the reaction of AnCl4(DME)n (An = Th, n = 2; U, n = 0) with 3 equiv of LiC6Cl5 in Et2O resulted in the formation of heteroleptic actinide-aryl "ate"complexes [Li(DME)2(Et2O)][Li(Et2O)2][ThCl3(C6Cl5)3] ([Li][3]) and [Li(Et2O)3][UCl2(C6Cl5)3] ([Li][4]). Density functional calculations show that the An-Cipso σ-bonds are considerably more covalent for the uranium complexes vs the thorium analogues, in line with past results. Additionally, good agreement between experiment and calculations is obtained for the 13Cipso NMR chemical shifts in [Li][1] and [Li][3]. The calculations demonstrate a deshielding by ca. 29 ppm from spin-orbit coupling effects originating at Th, which is a direct consequence of 5f orbital participation in the Th-C bonds.
- Autschbach, Jochen,Hayton, Trevor W.,Ordo?ez, Osvaldo,Wu, Guang,Yu, Xiaojuan
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supporting information
p. 12436 - 12444
(2021/08/24)
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- Novel B(Ar′)2(Ar″) hetero-tri(aryl)boranes: A systematic study of Lewis acidity
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A series of homo- and hetero-tri(aryl)boranes incorporating pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, and pentachlorophenyl groups, four of which are novel species, have been studied as the acidic component of frustrated Lewis pairs for the heterolytic cleavage of H2. Under mild conditions eight of these will cleave H2; the rate of cleavage depending on both the electrophilicity of the borane and the steric bulk around the boron atom. Electrochemical studies allow comparisons of the electrophilicity with spectroscopic measurements of Lewis acidity for different series of boranes. Discrepancies in the correlation between these two types of measurements, combined with structural characterisation of each borane, reveal that the twist of the aryl rings with respect to the boron-centred trigonal plane is significant from both a steric and electronic perspective, and is an important consideration in the design of tri(aryl)boranes as Lewis acids.
- Blagg, Robin J.,Simmons, Trevor R.,Hatton, Georgina R.,Courtney, James M.,Bennett, Elliot L.,Lawrence, Elliot J.,Wildgoose, Gregory G.
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p. 6032 - 6043
(2016/04/26)
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- PROCESS FOR PRODUCING METHANOL
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The present invention relates to a novel process for the production of methanol. The process comprises the heterolytic cleavage of hydrogen by a frustrated Lewis pair comprising a Lewis acid and a Lewis base; and the hydrogenation of CO2 with the heterolytically cleaved hydrogen to form methanol.
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Page/Page column 23-24
(2011/05/05)
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- The Dechlorination of Some Highly Chlorinated Naphthalene Derivatives
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The cycloadducts formed between tetrachlorobenzyne and a variety of arenes and cyclic 1,3-dienes have been reductively dechlorinated.The products are formally benzyne cycloadducts, many of which are difficult to make by other routes.High yields are obtained when sodium and t-butanol in boiling THF are used for the reduction.THF serves as a solvent but t-butanol not only acts as a proton donor but also appears to initiate the reduction.Tetrachlorobenzyne should be considered as an alternative reagent whenever benzyne itself appears to be required.
- Hales, Neil J.,Heaney, Harry,Hollinshead, John H.,Lai, Steven M. F.,Singh, Pritpal
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p. 7777 - 7790
(2007/10/02)
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