Solution Reactions of a Bis(pyrrolylaldiminate)copper(II) Complex with Peralkyl Zinc, Aluminum, and Boron Reagents: Investigation of the Pathways Responsible for Copper Metal Deposition

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• 作者：Balamurugan Vidjayacoumar ; David J. H. Emslie ; James M. Blackwell ; Scott B. Clendenning ; James F. Britten
• 刊名：Chemistry of Materials
• 出版年：2010
• 出版时间：September 14, 2010
• 年：2010
• 卷：22
• 期：17
• 页码：4854-4866
• 全文大小：1139K
• 年卷期：v.22,no.17(September 14, 2010)
• ISSN：1520-5002

文摘

The solution reactions of bis(N-isopropylpyrrolylaldiminate)copper(II) (CuL₂) with AlMe₃, BEt₃, and ZnEt₂ have been studied. In all cases, reduction occurs in two stages via a stable copper(I) pyrrolylaldiminate complex (Cu₂L₂), with each stage initiated by copper alkyl complex formation. Reduction from “LCuR” (R = Me or Et) occurs with release of R₂ or L−R, consistent with bimolecular C−C or C−N bond-forming reductive elimination. At room temperature or below, copper deposition from “CuMe” occurs exclusively via reductive elimination of ethane, whereas decomposition of “CuEt” yields ethylene, ethane, and hydrogen, indicative of both β-hydride elimination and reductive elimination. The reaction byproducts [Cu₂L₂], [LAlMe₂], [L₂AlMe], [AlL₃], [LBEt₂], [LZnEt], [ZnL₂], L−Me, and L−Et were synthesized independently and isolated as pure compounds. All compounds are thermally stable, with the exception of LZnEt, which undergoes ligand redistribution to form ZnL₂ and ZnEt₂ in solution and as a solid at elevated temperatures. With the exception of [LZnEt] and [Cu₂L₂], these complexes are also volatile; monoligated [LAlMe₂] and [LBEt₂] are particularly volatile, and therefore more desirable as byproducts in ALD or pulsed-CVD.