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Copper(I) tert-Butylthiolato Clusters as Single-Source Precursors for High-Quality Chalcocite Thin Films:  Precursor Chemistry in Solution and the Solid State

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posted on 29.05.2007, 00:00 by Sven Schneider, Alma Dzudza, Gabriele Raudaschl-Sieber, Tobin J. Marks
Polymeric (CuStBu) (1) undergoes reaction with trialkylphosphines to form the cuprous thiolato phosphine complexes [(CuStBu)4(PR3)2] (R = Me (2a), Et (2b)) in high yield. In contrast to 2b, in polar solvents (CH2Cl2, tetrahydrofuran), complex 2a is in equilibrium with the ion pair Cu(PMe3)4+Cu5(StBu)6- (3) and other species such as (CuStBu)x(PMe3)2 (x = 6 (4), 8 (5)). Clusters 24 were isolated analytically pure and fully characterized in solution by multinuclear nuclear magnetic resonance (NMR) spectroscopy and in the solid state by single-crystal X-ray diffraction and 31P magic angle spinning NMR spectroscopy, while the structure of compound 5 was determined by single-crystal X-ray diffraction. Thermal analysis (TGA/DTA) and examination of the volatile byproducts suggest stepwise phosphine loss and C−S bond cleavage by isobutene elimination as the predominant thermolysis pathways of this new Cu2S precursor class.