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Investigation of Nitrile Hydration Chemistry by Two Transition Metal Hydroxide Complexes: Mn–OH and Ni–OH Nitrile Insertion Chemistry
Herein we describe the synthesis of a series of nickel complexes, including the formation of [( iPr PN H P)Ni(PMe 3 )][BPh 4 ] ( iPr PN H P = HN(CH 2 CH 2 (PiPr 2 )) 2 ). The ability of this phosphine complex to perform the 1,2-addition of H 2 O to produce the Ni–OH species [( iPr PN H P)NiOH][BPh 4 ] has been investigated. The nucleophilicity of the hydroxide moiety of both [(iPrPNHP)NiOH][BPh4] and the previously reported ( iPr PN H P)MnOH(CO) 2 was investigated through the hydration of aryl and alkyl nitriles, leading to the formation of a number of metal carboxamide (RC(O)NH–) bonds. This reactivity generated complexes with the general structures of [( iPr PN H P)Ni(NHC(O)R)][BPh 4 ] for nickel and ( iPr PN H P)Mn(NHC(O)R)(CO) 2 for manganese. Under catalytic conditions, the hydration of nitriles using nickel complexes yielded only a single turnover. However, ( iPr PN H P)MnOH(CO) 2 produced several turnovers, and the reaction conditions were probed for optimization.
Evidence for the Coordination-Insertion Mechanism of Ethene Dimerization at Nickel Cations Exchanged onto Beta Molecular Sieves
Abstract not provided
Room-Temperature Electrochemical Fluoride (De)insertion into CsMnFeF[subscript 6]
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Elucidating the Limit of Li Insertion into the Spinel Li 4 Ti 5 O 12
Here in this work, we show that the well-known lithium-ion anode material, Li 4 Ti 5 O 12 , exhibits exceptionally high initial capacity of 310 mAh g –1 when it is discharged to 0.01 V. It maintains a reversible capacity of 230 mAh g –1 , far exceeding the “theoretical” capacity of 175 mAh g –1 when this anode is lithiated to the composition Li 7 Ti 5 O 12 . Neutron diffraction analyses identify that additional Li reversibly enters into the Li 7 Ti 5 O 12 to form Li 8 Ti 5 O 12 . density functional theory (DFT) calculations reveal the average potentials of the Li 4 Ti 5 O 12 to Li 7 Ti 5 O 12 step and the Li 7 Ti 5 O 12 to Li 8 Ti 5 O 12 step are 1.57 and 0.19 V, respectively, which are in excellent agreement with experimental results. Transmission electron microscopy (TEM) studies confirm that the irreversible capacity of Li 4 Ti 5 O 12 during its first cycle originates from the formation of a solid electrolyte interface (SEI) layer. This work clarifies the fundamental lithiation mechanism of the Li 4 Ti 5 O 12 , when lithiated to 0.01 V vs L
From 2D to 3D: Postsynthetic Pillar Insertion in Electrically Conductive MOF
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Water Adsorption and Insertion in MOF-5
Not Available