Monomerizing Alkali-Metal 3,5-Dimethylbenzyl Salts with Tris(N, N-dimethyl-2-aminoethyl)amine (Me6TREN): Structural and Bonding Implications

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• 作者：David R. Armstrong ; Matthew G. Davidson ; Daniel Garcia-Vivo ; Alan R. Kennedy ; Robert E. Mulvey ; Stuart D. Robertson
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：October 21, 2013
• 年：2013
• 卷：52
• 期：20
• 页码：12023-12032
• 全文大小：463K
• 年卷期：v.52,no.20(October 21, 2013)
• ISSN：1520-510X

文摘

The series of alkali-metal (Li, Na, K) complexes of the substituted benzyl anion 3,5-dimethylbenzyl (Me₂C₆H₃CH₂^{鈥?/sup>) derived from 1,3,5-trimethylbenzene (mesitylene) have been coerced into monomeric forms by supporting them with the tripodal tetradentate Lewis donor tris(N,N-dimethyl-2-aminoethyl)amine, [N(CH₂CH₂NMe₂)₃, Me₆TREN]. Molecular structure analysis by X-ray crystallography establishes that the cation鈥揳nion interaction varies as a function of the alkali-metal, with the carbanion binding to lithium mainly in a 蟽 fashion, to potassium mainly in a 蟺 fashion, with the interaction toward sodium being intermediate between these two extremes. This distinction is due to the heavier alkali-metal forcing and using the delocalization of negative charge into the aromatic ring to gain a higher coordination number in accordance with its size. Me₆TREN binds the metal in a 畏4 mode at all times. This coordination isomerism is shown by multinuclear NMR spectroscopy to also extend to the structures in solution and is further supported by density functional theory (DFT) calculations on model systems. A Me₆TREN stabilized benzyl potassium complex has been used to prepare a mixed-metal ate complex by a cocomplexation reaction with tBu₂Zn, with the benzyl ligand acting as an unusual ditopic 蟽/蟺 bridging ligand between the two metals, and with the small zinc atom relocalizing the negative charge back on to the lateral CH₂ arm to give a complex best described as a contacted ion pair potassium zincate.}