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The synthesis, structure, and reactivity of thorium oxo and sulfido metallocenes have been comprehensively studied. Heating of an equimolar mixture of the dimethyl metallocene [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)ThMe(2) (2) and the bis-amide metallocene [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)Th(NH-p-tolyl)(2) (3) in refluxing toluene results in the base-free imido thorium metallocene, [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)Th═N(p-tolyl) (4), which is a useful precursor for the preparation of oxo and sulfido thorium metallocenes [η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)](2)Th═E (E = O (5) and S (15)) by cycloaddition-elimination reaction with Ph(2)C═E (E = O, S) or CS(2). The oxo metallocene 5 acts as a nucleophile toward alkylsilyl halides, while sulfido metallocene 15 does not. The oxo metallocene 5 and sulfido metallocene 15 undergo a [2 + 2] cycloaddition reaction with Ph(2)CO, CS(2), or Ph(2)CS, but they show no reactivity with alkynes. Density functional theory (DFT) studies provide insights into the subtle interplay between steric and electronic effects and rationalize the experimentally observed reactivity patterns. A comparison between Th, U, and group 4 elements shows that Th(4+) behaves more like an actinide than a transition metal.

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Novel hydrogels with excellent mechanical properties have prompted applications in biomedical and other fields. The reported tough hydrogels are usually fabricated by complicated chemical and/or physical methods. To develop more facile fabrication methods is very important for the practical applications of tough hydrogels. We report a very simple yet novel method for fabricating tough hydrogels that are totally physically cross-linked by cooperative hydrogen bonding between a pre-existing polymer and an in situ polymerized polymer. In this work, tough hydrogels are prepared by heating aqueous acrylamide (AAm) solution in the presence of poly(Nvinylpyrrolidone) (PVP) but without any chemical initiators or covalent bonding cross-linking agents. Mechanical tests of the asprepared and swollen PVP-in situ-PAAm hydrogels show that they exhibit very high tensile strengths, high tensile extensibility, high compressive strengths, and low moduli. Comparative synthesis experiments, DSC characterization, and molecular modeling indicate that the formation of strong cooperative hydrogen bonding between the pre-existing PVP and the in situ formed PAAm chains contributes to the gel formation and the toughening of the hydrogels. The unique microstructure of the gels with evenly distributed flexible cross-linking sites and long polymer chains attached to them endow the hydrogels with an excellent mechanism of distributing the applied load.

Smart functional nanomaterials colorimetrically responsive to all-pH and a wide temperature range are urgently needed due to their widespread applications in biotechnology, drug delivery, diagnosis and optical sensing. Although graphene quantum dots possess remarkable advantages in biological applications, they are only stable in neutral or weak acidic solutions, and strong acidic or alkaline conditions invariably suppress or diminish the fluorescence intensity. Herein, we report a new type of water-soluble, multicolor fluorescent graphene quantum dot which is responsive to all-pH from 1 to 14 with the naked eye. The synthesis was accomplished by electrolysis of the graphite rod, followed by refluxing in a concentrated nitric and sulfuric acid mixed solution. We demonstrate the novel red fluorescence of quinone structures transformed from the lactone structures under strong alkaline conditions. The fluorescence of the resulting graphene quantum dots was also found to be responsive to the temperature changes, demonstrating their great potential as a dual probe of pH and temperature in complicated environments such as biological media.

The synthesis, structure, and reactivity of a base-free thorium terminal-imido metallocene have been comprehensively studied. Treatment of thorium metallocenes [{η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)}(2)ThMe(2)] and [{η(5)-1,3-(Me(3)C)(2)C(5)H(3)}(2)ThMe(2)] with RNH(2) gives diamides [{η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)}(2)Th(NHR)(2)] (R=Me (7), p-tolyl (8)) and [{η(5)-1,3-(Me(3)C)(2)C(5)H(3)}(2)Th(NH-p-tolyl)(2)] (9), respectively. Diamides 7 and 9 do not eliminate methylamine or p-toluidine, but sublime without decomposition at 150 °C under vacuum (0.01 mmHg), whereas diamide 8 is converted at 140 °C/0.01 mmHg into the primary amine p-tolyl-NH(2) and [{η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)}(2)Th=N(p-tolyl)] (10), which may be isolated in pure form. Imido metallocene 10 does not react with electrophiles such as alkylsilyl halides; however, it reacts with electron-rich or unsaturated reagents. For example, reaction of 10 with sulfur affords the metallacycle [{η(5)-1,2,4-(Me(3)C)(3)C(5)H(2)}(2)Th{N(p-tolyl)S-S}]. Imido 10 is an important intermediate in the catalytic hydroamination of internal alkynes, and an efficient catalyst for the trimerization of PhCN. Density functional theory (DFT) studies provide a detailed understanding of the experimentally observed reactivity patterns.

The synthesis, structure, and reactivity of an actinide metallacyclopropene were comprehensively studied. The reduction of [η(5)-1,2,4-(Me3C)3C5H2]2ThCl2 (1) with potassium graphite (KC8) in the presence of diphenylacetylene (PhC≡CPh) yields the first stable actinide metallacyclopropene [η(5)-1,2,4-(Me3C)3C5H2]2Th(η(2)-C2Ph2) (2). The magnetic susceptibility data show that 2 is indeed a diamagnetic Th(IV) complex, and density functional theory (DFT) studies suggest that the 5f orbitals contribute to the bonding of the metallacyclopropene Th-(η(2)-C═C) moiety. Complex 2 shows no reactivity toward alkynes, but it reacts with a variety of heterounsaturated molecules such as aldehyde, ketone, carbodiimide, nitrile, organic azide, and diazoalkane derivatives. DFT studies complement the experimental observations and provide additional insights. Furthermore, a comparison between Th and group 4 metals reveals that Th(4+) shows unique reactivity patterns.

This review concentrates on the results obtained thus far in cross-coupling reactions utilising Pd-PEPPSI-IPr (pre)catalyst. Results from computational studies expose possible factors behind the high reactivity of this complex, as well as mechanistic details for the IPr-Pd-mediated alkyl-alkyl Negishi cross-coupling.