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• W2007609528 abstract "The effect of the heteroleptic ligand sets {(C5Me5)2[iPrNC(Me)NiPr]}3− and {(C5Me5)2[(Me)NNN(Ad)]}3− on actinide−carbon bond reactivity has been evaluated by examining the monomethyl actinide metallocene amidinate complexes (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]AnMe (An = U, 1; Th, 2) and the triazenido complex (C5Me5)2[(Me)NNN(Ad)-κ2N1,3]UMe, 3. This has led to a facile method to convert methyl groups in U4+ and Th4+ complexes to halide and pseudo-halide ligands. Complexes 1 and 3 react with AgOSO2CF3 (AgOTf) to produce (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]U(OTf), 4, and (C5Me5)2[(Me)NNN(Ad)-κ2N1,3]U(OTf), 5, respectively. The methyl complexes are also reactive with copper reagents, as demonstrated by the reactions of CuI with 1 and 2 to make (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]UI, 6, and (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]ThI, 7, respectively. Similarly, reactions of CuBr with 1 and 3 generate (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]UBr, 8, and (C5Me5)2[(Me)NNN(Ad)-κ2N1,3]UBr, 9, respectively. These triflate and halide complexes are good precursors to other complexes with these ligand sets, as exemplified by their reactions with NaN3, which produce (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]U(N3), 10, and (C5Me5)2[(Me)NNN(Ad)-κ2N1,3]U(N3), 11, respectively. However, the reactions of 4 and 6 with LiCH2SiMe3 lead to reduction and the formation of the trivalent uranium heteroleptic metallocene (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]U, 12. LiCH2SiMe3 does not cause reduction with the triazenido ligand set, and the monoalkyl complex (C5Me5)2[(Me)NNN(Ad)-κ2N1,3]U(CH2SiMe3), 13, can be isolated." @default.
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• W2007609528 date "2009-12-08" @default.
• W2007609528 modified "2023-10-03" @default.
• W2007609528 title "Reactivity of Methyl Groups in Actinide Metallocene Amidinate and Triazenido Complexes with Silver and Copper Salts" @default.
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• W2007609528 doi "https://doi.org/10.1021/om9008179" @default.
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