Microsolvated and Chelated Butylzinc Cations: Formation,Relative Stability,and Unimolecular Gas‐Phase Chemistry |
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Authors: | Julia E. Fleckenstein Konrad Koszinowski Dr. |
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Affiliation: | Department Chemie und Biochemie, Ludwig‐Maximilians‐Universit?t München, Butenandtstrasse 5–13, 81377 München (Germany), Fax: (+49)?89‐21809977658 |
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Abstract: | 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′‐tetramethylethylenediamine), 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. |
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Keywords: | gas‐phase reactions ligand effects mass spectrometry solvent effects zinc |
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