Treatment of [{Ti(η5-C5Me5)(μ-O)}3(μ3-CR)] [R = H (1), Me (2)] with AlPh3 or AlMe3 gives adducts [R′3Al(μ3-O)(μ-O)2{Ti(η5-C5Me5)}3(μ3-CR)] [R = H, R′ = Ph (3), Me (4); R = Me, R′ = Ph (5), Me (6)] that react with LiNMe2 to give the contact ion pair complexes [Ph3Al(μ-NMe2)Li(μ3-O)3{Ti(η5-C5Me5)}3(μ3-CR)] [R = H (7), Me (8)] or the solvent-separated ion pair compounds [Li{(μ3-O)3Ti3(η5-C5Me5)3(μ3-CR)}2][(Me3Al)2(μ-NMe2)] [R = H (9), Me (10)]. Reactions of 1 or 2 with a mixture of AlPh3 and LiCH2SiMe3 lead to the solvent-separated ion pair complexes [Li{(μ3-O)3Ti3(η5-C5Me5)3(μ3-CR)}2][Al(CH2SiMe3)Ph3] [R = H (11), Me (12)], presumably by evolution of redistribution intermediates containing the lithium dicubane cation [Li{(μ3-O)3Ti3(η5-C5Me5)3(μ3-CR)}2]+ and [Li{Al(μ-Ph)2Ph(CH2SiMe3)}2]− anionic units. Surprisingly, reaction of 4 with p-tolyl lithium gives the complex [{Me2Al(μ-Me)Li(p-MeC6H4)}{(μ3-O)2(μ-O)Ti3(η5-C5Me5)3(μ3-CH)}] 13 in which the aryl lithium species is incorporated showing interactions with both the trialkyl aluminium unit and the organometallic oxide 1. X-ray diffraction studies were performed on 8, 12 and 13.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/c3dt32725f | DOI Listing |
Chem Sci
January 2025
Chemical Sciences Division, Oak Ridge National Laboratory Oak Ridge TN 37830 USA
The successful design and deployment of next-generation nuclear technologies heavily rely on thermodynamic data for relevant molten salt systems. However, the lack of accurate force fields and efficient methods has limited the quality of thermodynamic predictions from atomistic simulations. Here we propose an efficient free energy framework for computing chemical potentials, which is the central free energy quantity behind many thermodynamic properties.
View Article and Find Full Text PDFJ Colloid Interface Sci
January 2025
School of Materials Science and Engineering, Harbin Institute of Technology (Shenzhen), Shenzhen, Guangdong 518055, China. Electronic address:
Active colloids driven out of thermal equilibrium serve as building blocks for smart materials with tunable structures and functions. Using chemical energy to drive colloids is advantageous but requires precise control over chemical release. To address this, we developed colloidal ionogels-polymer microspheres infused with ionic liquids-that show controlled assembly and self-propulsion upon tunable swelling.
View Article and Find Full Text PDFActa Crystallogr B Struct Sci Cryst Eng Mater
February 2025
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, 2 Okólna, Wrocław, 50-422, Poland.
X-ray structural analysis of bis(guanidinium) disodium hypodiphosphate heptahydrate, (CHN)Na(PO)·7HO revealed close Na...
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München, Germany.
Free ions in organic solvents of low polarity would be valuable tools for the activation of low-reactivity substrates. However, the formation of unreactive ion pairs at concentrations relevant for synthesis has prevented the success of this concept so far. On the example of highly nucleophilic pyridinamide phosphonium salts in dichloromethane, we show that asymmetric aggregation offers a solution to this general problem.
View Article and Find Full Text PDFInorg Chem
January 2025
College of Chemistry, Sichuan University, Chengdu 610065, P. R. China.
We present two novel antimony(III)-based tellurite sulfate crystals, Sb(TeO)(SO)-1̅ (I) and Sb(TeO)(SO)-2/ (II), synthesized using a dual lone pair strategy that incorporates Sb and Te ions into a sulfate framework. This approach significantly enhances the birefringence of these compounds, with values of 0.11 and 0.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!