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首页> 外文期刊>Chemistry: A European journal >Microsolvated and Chelated Butylzinc Cations: Formation, Relative Stability, and Unimolecular Gas-Phase Chemistry
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Microsolvated and Chelated Butylzinc Cations: Formation, Relative Stability, and Unimolecular Gas-Phase Chemistry

机译：微溶剂化和螯合的丁基锌阳离子：形成，相对稳定性和单分子气相化学。

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Solutions of butylzinc iodide in tetrahydrofuran, acetonitrile, and N,N-dimethylformamide were analyzed by electrospray ionization mass spectrometry. In all cases, microsolvated butylzinc cations [ZnBu(solvent)(n)](+), n = 1-3, were detected. The parallel observation of the butylzincate anion [ZnBuI2](-) suggests that these ions result from disproportionation of neutral butylzinc iodide in solution. In the presence of simple bidentate ligands (1,2-dimethoxyethane, N,N-dimethyl-2-methoxyethylamine, and N,N,N',N'-tet-ramethylethylenediamine), chelate complexes of the type [ZnBu(ligand)](+) form quite readily. The relative stabilities of these complexes were probed by competition experiments and analysis of their unimolecular gas-phase reactivity. Fragmentation of mass-selected [ZnBu(ligand)](+) leads to the elimination of butene and formation of [ZnH-(ligand)](+). In marked contrast, the microsolvated cations [ZnBu(solvent)(n)](+) lose the attached solvent molecules upon gas-phase fragmentation to produce bare [ZnBu](+), which subsequently dissociates into [C4H9](+) and Zn. This difference in reactivity resembles the situation in organozinc solution chemistry, in which chelating ligands are needed to activate dialkylzinc compounds for the nucleophilic addition to aldehydes.
机译：通过电喷雾电离质谱分析丁基碘化锌在四氢呋喃，乙腈和N，N-二甲基甲酰胺中的溶液。在所有情况下，均检测到微溶剂化的丁基锌阳离子[ZnBu（溶剂）（n）]（+），n = 1-3。丁基锌酸盐阴离子[ZnBuI2]（-）的平行观察表明，这些离子是由于中性丁基碘化锌在溶液中的歧化所致。在简单的双齿配体（1,2-二甲氧基乙烷，N，N-二甲基-2-甲氧基乙胺和N，N，N'，N'-四氟甲基甲基乙二胺）的存在下，螯合[ZnBu（配体） ]（+）很容易形成。通过竞争实验和对它们的单分子气相反应性的分析来探究这些配合物的相对稳定性。质量选择的[ZnBu（配体）]（+）的断裂导致丁烯的消除和[ZnH-（配体）]（+）的形成。与之形成鲜明对比的是，微溶剂化的阳离子[ZnBu（溶剂）（n）]（+）在气相裂解后会失去附着的溶剂分子，从而生成裸露的[ZnBu]（+），随后分解为[C4H9]（+）和锌反应性的这种差异类似于有机锌溶液化学中的情况，在这种情况下，需要螯合配体来活化二烷基锌化合物以亲核加成醛。

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