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Main group multiple C-H/N-H bond activation of a diamine and isolation of a molecular dilithium zincate hydride : experimental and DFT evidence for Alkali metal-zinc synergistic effects

Campbell, Ross and Cannon, Daniel and Garcia-Alvarez, Pablo and Kennedy, Alan R. and Mulvey, Robert E. and Robertson, Stuart D. and Sassmannshausen, Joerg and Tuttle, Tell (2011) Main group multiple C-H/N-H bond activation of a diamine and isolation of a molecular dilithium zincate hydride : experimental and DFT evidence for Alkali metal-zinc synergistic effects. Journal of the American Chemical Society, 133 (34). pp. 13706-13717. ISSN 0002-7863

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Abstract

The surprising transformation of the saturated diamine (iPr)NHCH2CH2NH(iPr) to the unsaturated diazaethene [(iPr)NCH=CHN(iPr)](2-) via the synergic mixture nBuM, (tBu)(2)Zn and TMEDA (where M = Li, Na; TMEDA = N, N,N',N'-tetramethylethylenediamine) has been investigated by multinuclear NMR spectroscopic studies and DFT calculations. Several pertinent intermediary and related compounds (TMEDA)Li[(iPr)NCH2CH2NH(iPr)]Zn(tBu)(2) (3), (TMEDA)Li[(iPr)NCH2CH2N(iPr)]Zn(tBu) (5), {(THF)Li[(iPr)NCH2CH2N(iPr)]Zn(tBu)}(2) (6), and {(TMEDA)Na[(iPr)NCH2CH2N(iPr)]Zn(tBu)}(2) (11), characterized by single-crystal X-ray diffraction, are discussed in relation to their role in the formation of (TMEDA)M[(iPr)NCH=CHN(iPr)]Zn(tBu) (M = Li, 1; Na, 10). In addition, the dilithio zincate molecular hydride [(TMEDA)Li](2)[(iPr)NCH2CH2N(iPr)]Zn(tBu)H 7 has been synthesized from the reaction of (TMEDA)Li[(iPr)NCH2CH2NH(iPr)]Zn(tBu)(2) 3 with nBuLi(TMEDA) and also characterized by both X-ray crystallographic and NMR spectroscopic studies. The retention of the Li-H bond of 7 in solution was confirmed by Li-7-H-1 HSQC experiments. Also, the Li-7 NMR spectrum of 7 in C6D6 solution allowed for the rare observation of a scalar (1)J(Li-H) coupling constant of 13.3 Hz. Possible mechanisms for the transformation from diamine to diazaethene, a process involving the formal breakage of four bonds, have been determined computationally using density functional theory. The dominant mechanism, starting from (TMEDA)Li[(iPr)NCH2CH2N(iPr)]Zn(tBu) (4), involves the formation of a hydride intermediate and leads directly to the observed diazaethene product. In addition the existence of 7 in equilibrium with 4 through the dynamic association and dissociation of a (TMEDA)LiH ligand, also provides a secondary mechanism for the formation of the diazaethene. The two reaction pathways (i.e., starting from 4 or 7) are quite distinct and provide excellent examples in which the two distinct metals in the system are able to interact synergically to catalyze this otherwise challenging transformation.

Item type: Article
ID code: 35456
Keywords: directed ortho-metalation, halogen-magnesium exchange, mixed lithium-cadmium, alpha-diimine ligands, enantioselective conjugate addition, cross-coupling reactions, tertiary aromatic amide, large-scale preparation, sodium TMP-zincate, mediated zincation, Chemistry, Biochemistry, Colloid and Surface Chemistry, Chemistry(all), Catalysis
Subjects: Science > Chemistry
Department: Faculty of Science > Pure and Applied Chemistry
Technology and Innovation Centre > Bionanotechnology
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Depositing user: Pure Administrator
Date Deposited: 31 Oct 2011 15:24
Last modified: 10 Oct 2014 04:37
URI: http://strathprints.strath.ac.uk/id/eprint/35456

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