3 years ago

Ruthenocene Precursors for Ruthenium-Containing Thin-Film Deposition: An Example of Solvent Nucleophilic Attack on Fulvene

Ruthenocene Precursors for Ruthenium-Containing Thin-Film Deposition: An Example of Solvent Nucleophilic Attack on Fulvene
Seung Uk Son, Bo Keun Park, Taek-Mo Chung, Jeong Hwan Han, Ga Yeon Lee, Seong Ho Han, Eun Ae Jung, Chang Gyoun Kim, Sheby Mary George
A new series of ruthenocene complexes were prepared from RuCl3·xH2O and 6,6-dimethylfulvene as potential precursors for thin-film deposition. The formation of these complexes was the result of an unforeseen nucleophilic attack of the solvent molecules (alcohols/amines) on the 6,6-dimethylfulvene ligand during the reaction. Complexes [RuII(C5H4C(CH3)2OCH3)2] (1), [RuII(C5H4C(CH3)2OC2H5)2] (2), [RuII(C5H4C(CH3)2N(CH3)2)2] (3), and [RuII(C5H4C(CH3)2N(CH2CH3)2)2] (4) were isolated in pure form and characterized by Fourier transform (FT) infrared and FT nuclear magnetic resonance spectroscopy as well as elemental and thermogravimetric (TG) analyses. Crystallographic studies of complexes 13 revealed a monomeric ruthenocene structure for all complexes and showed that the deprotonated alkylalkoxide or dialkylamide of the solvent molecule was attached to the exocyclic carbon of the fulvene ligand. Although the complexes were formed as ruthenocenes instead of the expected ruthenium fulvene complexes, they all displayed excellent stabilities and thermal properties. In particular, complexes 3 and 4 emerged as the best compounds owing to their clean TGA plot and excellent volatility, holding the potential as precursors for thin-film deposition.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00238

DOI: 10.1021/acs.organomet.7b00238

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