- Highly selective sp3 C-N bond activation of tertiary anilines modulated by steric and thermodynamic factors
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A highly selective sp3 C-N cleavage of tertiary anilines was achieved using the TBN/TEMPO catalyst system. When N,N-diaklylanilines (alkyl, benzyl) were employed, the N-CH3 bond was selectively cleaved via radical C-H activation. Moreover, when the allyl group was installed, totally reverse selectivity was observed. It is worth noting that the solvent effect is also crucial to obtain high reaction efficiency and selectivity.
- Jia, Xiaodong,Li, Pengfei,Shao, Yu,Yuan, Yu,Ji, Honghe,Hou, Wentao,Liu, Xiaofei,Zhang, Xuewen
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supporting information
p. 5568 - 5574
(2017/12/06)
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- Synthetic derivatives of mauveine
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Oxidation of phenosafranin and an excess of aniline gave a novel hydroxylated derivative of pseudo-mauveine. N-Methyl-p-toluidine and bis(4-methylphenyl)amine are efficient building blocks for making mauveine-related chromophores. Their oxidation with Ks
- Plater, M. John,Harrison, William T.A.
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p. 427 - 434
(2013/09/12)
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- Groups 5 and 6 terminal hydrazido(2-) complexes: Nβ substituent effects on ligand-to-metal charge-transfer energies and oxidation states
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Brightly colored terminal hydrazido(2-) (dme)MCl3(NNR 2) (dme = 1,2-dimethoxyethane; M = Nb, Ta; R = alkyl, aryl) or (MeCN)WCl4(NNR2) complexes have been synthesized and characterized. Perturbing the electronic environment of the β (NR 2) nitrogen affects the energy of the lowest-energy charge-transfer (CT) transition in these complexes. For group 5 complexes, increasing the energy of the Nβ lone pair decreases the ligand-to-metal CT (LMCT) energy, except for electron-rich niobium dialkylhydrazides, which pyramidalize Nβ in order to reduce the overlap between the Nb=N α π bond and the Nβ lone pair. For W complexes, increasing the energy of Nβ eventually leads to reduction from formally [WVI≡N-NR2] with a hydrazido(2-) ligand to [WIV=N=NR2] with a neutral 1,1-diazene ligand. The photophysical properties of these complexes highlight the potential redox noninnocence of hydrazido ligands, which could lead to ligand- and/or metal-based redox chemistry in early transition metal derivatives.
- Tonks, Ian A.,Durrell, Alec C.,Gray, Harry B.,Bercaw, John E.
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supporting information; experimental part
p. 7301 - 7304
(2012/06/16)
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