10.1021/om0003887.s001
Hideo Nagashima
Hideo
Nagashima
Akihiro Suzuki
Akihiro
Suzuki
Takafumi Iura
Takafumi
Iura
Kazuhiro Ryu
Kazuhiro
Ryu
Kouki Matsubara
Kouki
Matsubara
Stoichiometric and Catalytic Activation of Si−H Bonds
by a Triruthenium Carbonyl Cluster,
(μ<sub>3</sub>,η<sup>2</sup>:η<sup>3</sup>:η<sup>5</sup>-acenaphthylene)Ru<sub>3</sub>(CO)<sub>7</sub>: Isolation of the
Oxidative Adducts, Catalytic Hydrosilylation of
Aldehydes, Ketones, and Acetals, and Catalytic
Polymerization of Cyclic Ethers
American Chemical Society
2000
Oxidative Adducts
CO ligand
cyclic ether
trialkylsilanes results
NMR studies
THF
representative example
4 O
Mechanistic considerations
Catalytic Polymerization
Catalytic Activation
catalysts 1
cyclic ethers
silyl ethers
Cyclic Ethers Treatment
Triruthenium Carbonyl Cluster
M n
CH
RhCl
ketone
oxidative addition
stoichiometric amounts
Catalytic Hydrosilylation
acenaphthylene
hydrosilylation
Compound 1 catalyzes
NMR spectroscopy
HSiR 3
carbonyl compounds
room temperature
2000-08-05 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Stoichiometric_and_Catalytic_Activation_of_Si_H_Bonds_by_a_Triruthenium_Carbonyl_Cluster_sub_3_sub_sup_2_sup_sup_3_sup_sup_5_sup_-acenaphthylene_Ru_sub_3_sub_CO_sub_7_sub_Isolation_of_the_Oxidative_Adducts_Catalytic_Hydrosilylation_of_Aldehydes_Ketones_an/3762990
Treatment of the ruthenium cluster (μ<sub>3</sub>,η<sup>2</sup>:η<sup>3</sup>:η<sup>5</sup>-acenaphthylene)Ru<sub>3</sub>(CO)<sub>7</sub> (<b>1</b>) with stoichiometric amounts of trialkylsilanes results in liberation of a CO ligand followed by
oxidative addition of a Si−H bond. The trinuclear silyl complexes (μ<sub>3</sub>,η<sup>2</sup>:η<sup>3</sup>:η<sup>5</sup>-acenaphthylene)Ru<sub>3</sub>(H)(SiR<sub>3</sub>)(CO)<sub>6</sub> (<b>2</b>) were isolated in good yield. They were characterized by NMR
spectroscopy and X-ray crystallography. Compound <b>1 </b>catalyzes the hydrosilylation of olefins,
acetylenes, ketones, and aldehydes. In particular, the reactions of aldehydes and ketones
proceed at room temperature to form the corresponding silyl ethers in good yield; the catalytic
activities are superior to those with RhCl(PPh<sub>3</sub>)<sub>3</sub>. The RhCl(PPh<sub>3</sub>)<sub>3</sub>-catalyzed hydrosilylation
of ketones with Me<sub>2</sub>(H)SiCH<sub>2</sub>CH<sub>2</sub>Si(H)Me<sub>2</sub> results in selective reaction of only one Si−H
terminus, while similar reactions, when catalyzed by <b>1</b>, allow utilization of both Si−H groups.
Significantly different regio- and stereoselectivities, compared with those obtained in
reactions catalyzed by RhCl(PPh<sub>3</sub>)<sub>3</sub>, also were observed in the hydrosilylation of α,β-unsaturated carbonyl compounds and 4-<i>tert</i>-butylcyclohexanone, respectively. The reactions
with acetals and cyclic ethers also take place under similar conditions. The reaction of
trialkylsilanes with an excess of a cyclic ether resulted in ring-opening polymerization.
Polymerization of THF was investigated as a representative example. Treatment of
trialkylsilanes with an excess of THF (10−10<sup>2</sup> equiv with respect to silanes) in the presence
of a catalytic amount of <b>1</b> resulted in production of polytetrahydrofuran with <i>M</i><sub>n</sub> = 1000−200 000 and <i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> = 1.3−2.0. Changing the ratio of THF to HSiR<sub>3</sub> can control the molecular
weight. NMR studies suggested that the structure of the polymer is R<sub>3</sub>SiO−[(CH<sub>2</sub>)<sub>4</sub>O]<i><sub>n</sub></i>−CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>3</sub>. Mechanistic considerations based on differences in the catalytic activities
between the catalysts <b>1</b> and <b>2</b> are discussed.