Synthesis of two new Mo(II) organometallic catalysts immobilized on POSS for application in olefin oxidation reactions

Article abstract of DOI:10.1016/j.jorganchem.2017.02.010

The purpose of this work was the preparation and characterization of two new catalysts POSS-ATZAc-[Mo(η³-C₃H₅)Br(CO)₂] (POSS-Mo-I) and POSS-ATZAc-[Mo(CO)₃Br₂] (POSS-Mo-II). The new heterogeneous catalysts were characterized by several techniques and used as catalysts for the epoxidation of olefins, presenting high catalytic activity. To study and optimize the syntheses of the heterogeneous catalysts, immobilization experiments of the [Mo(η³-C₃H₅)Br(CO)₂(NCMe)₂] and [Mo(CO)₃Br₂(NCMe)₂] organometallic complexes on the modified polyhedral oligomeric silsesquioxane were performed. The sorption properties of the modified silsesquioxane showed to be dependent of the contact time, concentration and temperature. Catalysts were tested in the epoxidation of six olefins and compared with homogeneous species [Mo(η³-C₃H₅)Br(CO)₂(ATZAc)] (Mo-I) and [Mo(CO)₃Br₂(ATZAc)] (Mo-II). To the best of our knowledge, this paper is the first that has reported the preparation and characterization of two new heterogeneous catalysts, as well as the comparison with homogeneous species for catalytic epoxidation of olefins.

Full text of DOI:10.1016/j.jorganchem.2017.02.010

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.
Accepted Manuscript
Synthesis of two new Mo(II) organometallic catalysts immobilized on POSS for
application in olefin oxidation reactions
Eduardo Guimarães Vieira, Alexandre Gonçalves Dal-Bó, Tiago Elias Allievi Frizon,
Newton Luiz Dias Filho
PII:
S0022-328X(17)30080-3
10.1016/j.jorganchem.2017.02.010
JOM 19799
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 22 November 2016
Revised Date: 31 January 2017
Accepted Date: 9 February 2017
Please cite this article as: E.G. Vieira, A.G. Dal-Bó, T.E.A. Frizon, N.L. Dias Filho, Synthesis of two new
Mo(II) organometallic catalysts immobilized on POSS for application in olefin oxidation reactions, Journal
of Organometallic Chemistry (2017), doi: 10.1016/j.jorganchem.2017.02.010.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.
ACCEPTED MANUSCRIPT

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.
ACCEPTED MANUSCRIPT
Synthesis of two new Mo(II) organometallic catalysts immobilized on POSS for
application in olefin oxidation reactions
Eduardo Guimarães Vieira,a* Alexandre Gonçalves Dal-Bó,b Tiago Elias Allievi Frizonb
and Newton Luiz Dias Filhoa,b**
aDepartamento de Física e Química, Unesp-Univ Estadual Paulista, Av. Brasil, 56-
Centro, Caixa Postal 31, 15385-000 Ilha Solteira, São Paulo, Brazil.
bUniversidade do Extremo Sul Catarinense, Av. Universitária, 1105, CP 3167, CEP
88806-000, Criciúma, Santa Catarina, Brazil.
Correspondence to: **N. L. Dias Filho (E-mail: nldias@unesc.net) Tel: +55 48
91048415 and *E.G. Vieira (E-mail: eduardogv5007@gmail.com)

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.
ACCEPTED MANUSCRIPT
Abstract
The purpose of this work was the preparation and characterization of two new catalysts
POSS-ATZAc-[Mo(η3-C3H5)Br(CO)2] (POSS-Mo-I) and POSS-ATZAc-[Mo(CO)3Br2]
(POSS-Mo-II). The new heterogeneous catalysts were characterized by several
techniques and used as catalysts for the epoxidation of olefins, presenting high catalytic
activity. To study and optimize the syntheses of the heterogeneous catalysts,
immobilization experiments of the [Mo(η3-C3H5)Br(CO)2(NCMe)2] and
[Mo(CO)3Br2(NCMe)2] organometallic complexes on the modified polyhedral
oligomeric silsesquioxane were performed. The sorption properties of the modified
silsesquioxane showed to be dependent of the contact time, concentration and
temperature. Catalysts were tested in the epoxidation of six olefins and compared with
homogeneous species [Mo(η3-C3H5)Br(CO)2(ATZAc)] (Mo-I) and
[Mo(CO)3Br2(ATZAc)] (Mo-II). To the best of our knowledge, this paper is the first
that has reported the preparation and characterization of two new heterogeneous
catalysts, as well as the comparison with homogeneous species for catalytic epoxidation
of olefins.
Keywords: Molybdenum complexes; Modified silsesquioxane; Catalysts; Epoxidation
of olefins.