Copper(I) carbene hydride complexes acting both as reducing agent and precursor for Cu ALD: a study through density functional theory

• Published in: Theoretical chemistry accounts Vol. 133; no. 1
• Main Authors: Dey, Gangotri, Elliott, Simon D.
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 2014
• Subjects: Atomic/Molecular Structure and Spectra; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Modeling Chemical Vapor Deposition and Atomic Layer Deposition; Organic Chemistry; Physical Chemistry; Regular Article; Theoretical and Computational Chemistry; ALD; Cu; DFT; Carbene hydride
• ISSN: 1432-881X; 1432-2234
• DOI: 10.1007/s00214-013-1416-y

We propose dual functional copper complexes that may act both as reducing agents and as Cu sources for prospective Cu atomic layer deposition. The example here is a CuH carbene complex, which can donate the H − anion to another Cu precursor forming neutral by-products and metallic Cu(0). We compute that such a reaction is thermodynamically possible because the Cu–H bond is weaker than that of Cu–C (from the carbene). Most other neutral ligands such as PPh 3 and BEt 3 show opposite order of bond strengths. We also find that substitution in the carbene by electronegative groups reduces the Cu–H bond strength. This further facilitates the donation of H − to the surface. The most promising copper carbene precursor is computed to be 1,3-diphenyl-4,5-imidazolidinedithione copper hydride (S-NHC)–CuH.