Synthesis of [Ru(CO)2(PPh3)(SP)] and [Ru(CO)(PPh3)2(SP)] and their catalytic activities for the hydroamination of phenylacetylene

Eiichiro Mizushima; Naoto Chatani; Fumitoshi Kakiuchi

doi:10.1016/j.jorganchem.2006.09.015

Synthesis of [Ru(CO)₂(PPh₃)(SP)] and [Ru(CO)(PPh₃)₂(SP)] and their catalytic activities for the hydroamination of phenylacetylene

Eiichiro Mizushima, Naoto Chatani, Fumitoshi Kakiuchi

Department of Chemistry

Research output: Contribution to journal › Article

14 Citations (Scopus)

Abstract

The reaction of [Ru(CO)₂(PPh₃)₃] (1) with o-styryldiphenylphophine (SP) (2) gave [Ru(CO)₂(PPh₃)(SP)] (3) in 83% yield. This styrylphosphine ruthenium complex 3 can also be synthesized by the reaction of [Ru(p-MeOC₆H₄NN)(CO)₂(PPh₃) ₂]BF₄ (4) with NaBH₄ and 2 in 50% yield. When "Ru(CO)(PPh₃)₃" generated by the reaction of [RuH₂(CO)(PPh₃)₃] (8) with trimethylvinylsilane reacted with 2, [Ru(CO)(PPh₃)₂(SP)] (10) was produced in moderate yield as an air sensitive solid. The spectral and X-ray data of these complexes revealed that the coordination geometries around the ruthenium center of both complexes corresponded to a distorted trigonal bipyramid with the olefin occupying the equatorial position and the C-C bonding in the olefin moiety in 3 and 10 contained a significant contribution from a ruthenacyclopropane limiting structure. Complexes 3 and 10 showed catalytic activity for the hydroamination of phenylacetylene 11 with aniline 12. Ruthenium complex 3 in the co-presence of NH₄PF₆ or H₃PW₁₂O₄₀ proves to be a superior catalyst system for this hydroamination reaction. In the case of the reaction using H₃PW₁₂O₄₀ as an additive, ketimines (13) was obtained in 99% yield at a ruthenium-catalyst loading of 0.1 mol%. Some aniline derivatives such as 4-methoxy, 4-trifluoromethyl-, and 4-bromoanilines can also be used in this hydroamination reaction.

Original language	English
Pages (from-to)	5739-5745
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	691
Issue number	26
DOIs	https://doi.org/10.1016/j.jorganchem.2006.09.015
Publication status	Published - 2006 Dec 15

Keywords

Anilines
Hydroamination
Phenylacetylene
Zero-valent ruthenium complexes
o-Styrylphosphine

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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Mizushima, E., Chatani, N., & Kakiuchi, F. (2006). Synthesis of [Ru(CO)₂(PPh₃)(SP)] and [Ru(CO)(PPh₃)₂(SP)] and their catalytic activities for the hydroamination of phenylacetylene. Journal of Organometallic Chemistry, 691(26), 5739-5745. https://doi.org/10.1016/j.jorganchem.2006.09.015

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title = "Synthesis of [Ru(CO)2(PPh3)(SP)] and [Ru(CO)(PPh3)2(SP)] and their catalytic activities for the hydroamination of phenylacetylene",

abstract = "The reaction of [Ru(CO)2(PPh3)3] (1) with o-styryldiphenylphophine (SP) (2) gave [Ru(CO)2(PPh3)(SP)] (3) in 83% yield. This styrylphosphine ruthenium complex 3 can also be synthesized by the reaction of [Ru(p-MeOC6H4NN)(CO)2(PPh3) 2]BF4 (4) with NaBH4 and 2 in 50% yield. When {"}Ru(CO)(PPh3)3{"} generated by the reaction of [RuH2(CO)(PPh3)3] (8) with trimethylvinylsilane reacted with 2, [Ru(CO)(PPh3)2(SP)] (10) was produced in moderate yield as an air sensitive solid. The spectral and X-ray data of these complexes revealed that the coordination geometries around the ruthenium center of both complexes corresponded to a distorted trigonal bipyramid with the olefin occupying the equatorial position and the C-C bonding in the olefin moiety in 3 and 10 contained a significant contribution from a ruthenacyclopropane limiting structure. Complexes 3 and 10 showed catalytic activity for the hydroamination of phenylacetylene 11 with aniline 12. Ruthenium complex 3 in the co-presence of NH4PF6 or H3PW12O40 proves to be a superior catalyst system for this hydroamination reaction. In the case of the reaction using H3PW12O40 as an additive, ketimines (13) was obtained in 99% yield at a ruthenium-catalyst loading of 0.1 mol%. Some aniline derivatives such as 4-methoxy, 4-trifluoromethyl-, and 4-bromoanilines can also be used in this hydroamination reaction.",

keywords = "Anilines, Hydroamination, Phenylacetylene, Zero-valent ruthenium complexes, o-Styrylphosphine",

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T1 - Synthesis of [Ru(CO)2(PPh3)(SP)] and [Ru(CO)(PPh3)2(SP)] and their catalytic activities for the hydroamination of phenylacetylene

AU - Mizushima, Eiichiro

AU - Chatani, Naoto

AU - Kakiuchi, Fumitoshi

PY - 2006/12/15

Y1 - 2006/12/15

N2 - The reaction of [Ru(CO)2(PPh3)3] (1) with o-styryldiphenylphophine (SP) (2) gave [Ru(CO)2(PPh3)(SP)] (3) in 83% yield. This styrylphosphine ruthenium complex 3 can also be synthesized by the reaction of [Ru(p-MeOC6H4NN)(CO)2(PPh3) 2]BF4 (4) with NaBH4 and 2 in 50% yield. When "Ru(CO)(PPh3)3" generated by the reaction of [RuH2(CO)(PPh3)3] (8) with trimethylvinylsilane reacted with 2, [Ru(CO)(PPh3)2(SP)] (10) was produced in moderate yield as an air sensitive solid. The spectral and X-ray data of these complexes revealed that the coordination geometries around the ruthenium center of both complexes corresponded to a distorted trigonal bipyramid with the olefin occupying the equatorial position and the C-C bonding in the olefin moiety in 3 and 10 contained a significant contribution from a ruthenacyclopropane limiting structure. Complexes 3 and 10 showed catalytic activity for the hydroamination of phenylacetylene 11 with aniline 12. Ruthenium complex 3 in the co-presence of NH4PF6 or H3PW12O40 proves to be a superior catalyst system for this hydroamination reaction. In the case of the reaction using H3PW12O40 as an additive, ketimines (13) was obtained in 99% yield at a ruthenium-catalyst loading of 0.1 mol%. Some aniline derivatives such as 4-methoxy, 4-trifluoromethyl-, and 4-bromoanilines can also be used in this hydroamination reaction.

AB - The reaction of [Ru(CO)2(PPh3)3] (1) with o-styryldiphenylphophine (SP) (2) gave [Ru(CO)2(PPh3)(SP)] (3) in 83% yield. This styrylphosphine ruthenium complex 3 can also be synthesized by the reaction of [Ru(p-MeOC6H4NN)(CO)2(PPh3) 2]BF4 (4) with NaBH4 and 2 in 50% yield. When "Ru(CO)(PPh3)3" generated by the reaction of [RuH2(CO)(PPh3)3] (8) with trimethylvinylsilane reacted with 2, [Ru(CO)(PPh3)2(SP)] (10) was produced in moderate yield as an air sensitive solid. The spectral and X-ray data of these complexes revealed that the coordination geometries around the ruthenium center of both complexes corresponded to a distorted trigonal bipyramid with the olefin occupying the equatorial position and the C-C bonding in the olefin moiety in 3 and 10 contained a significant contribution from a ruthenacyclopropane limiting structure. Complexes 3 and 10 showed catalytic activity for the hydroamination of phenylacetylene 11 with aniline 12. Ruthenium complex 3 in the co-presence of NH4PF6 or H3PW12O40 proves to be a superior catalyst system for this hydroamination reaction. In the case of the reaction using H3PW12O40 as an additive, ketimines (13) was obtained in 99% yield at a ruthenium-catalyst loading of 0.1 mol%. Some aniline derivatives such as 4-methoxy, 4-trifluoromethyl-, and 4-bromoanilines can also be used in this hydroamination reaction.

KW - Anilines

KW - Hydroamination

KW - Phenylacetylene

KW - Zero-valent ruthenium complexes

KW - o-Styrylphosphine

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