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

Eun Ae Jung; Sheby Mary George; Seong Ho Han; Ga Yeon Lee; Bo Keun Park; Jeong Hwan Han; Seung Uk Son; Chang Gyoun Kim; Taek Mo Chung

doi:10.1021/acs.organomet.7b00238

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

Eun Ae Jung, Sheby Mary George, Seong Ho Han, Ga Yeon Lee, Bo Keun Park, Jeong Hwan Han, Seung Uk Son, Chang Gyoun Kim, Taek Mo Chung

Dept. of Materials Science & Engineering

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

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 [Ru^II(C₅H₄C(CH₃)₂OCH₃)₂] (1), [Ru^II(C₅H₄C(CH₃)₂OC₂H₅)₂] (2), [Ru^II(C₅H₄C(CH₃)₂N(CH₃)₂)₂] (3), and [Ru^II(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 1-3 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.

Original language	English
Pages (from-to)	2755-2760
Number of pages	6
Journal	Organometallics
Volume	36
Issue number	15
DOIs	https://doi.org/10.1021/acs.organomet.7b00238
State	Published - 14 Aug 2017

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@article{5f44d6eca99e431093c25b5945815d6d,

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

abstract = "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 1-3 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.",

author = "Jung, \{Eun Ae\} and George, \{Sheby Mary\} and Han, \{Seong Ho\} and Lee, \{Ga Yeon\} and Park, \{Bo Keun\} and Han, \{Jeong Hwan\} and Son, \{Seung Uk\} and Kim, \{Chang Gyoun\} and Chung, \{Taek Mo\}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = aug,

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doi = "10.1021/acs.organomet.7b00238",

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T1 - Ruthenocene Precursors for Ruthenium-Containing Thin-Film Deposition

T2 - An Example of Solvent Nucleophilic Attack on Fulvene

AU - Jung, Eun Ae

AU - George, Sheby Mary

AU - Han, Seong Ho

AU - Lee, Ga Yeon

AU - Park, Bo Keun

AU - Han, Jeong Hwan

AU - Son, Seung Uk

AU - Kim, Chang Gyoun

AU - Chung, Taek Mo

PY - 2017/8/14

Y1 - 2017/8/14

N2 - 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 1-3 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.

AB - 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 1-3 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.

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U2 - 10.1021/acs.organomet.7b00238

DO - 10.1021/acs.organomet.7b00238

M3 - Article

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SN - 0276-7333

VL - 36

SP - 2755

EP - 2760

JO - Organometallics

JF - Organometallics

IS - 15

ER -

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

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