Peripheral SH-functionalisation of carbosilane dendrimers including the synthesis of the model compound dimethylbis(propanethiol)silane and their interaction with rhodium complexes (original) (raw)
* Corresponding authors
a Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, C.S.I.C.-Universidad de Zaragoza, E-50009 Zaragoza, (Spain)
E-mail: mciriano@ unizar.es
Fax: 34 976 761187
Tel: 34 976 761148
b Instituto Universitario de Catálisis Homogénea, Universidad de Zaragoza, 50009 Zaragoza, (Spain)
E-mail: mcasado@unizar.es
Tel: 34 976 762284
Abstract
Treatment of the allyl-containing compounds Me2Si(CH2CH![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
CH2)2 and MeSi(CH2CHCH2)3 with thioacetic acid in the presence of AIBN gave Me2Si[(CH2)3SC(O)CH3]2 and MeSi[(CH2)3SC(O)CH3]3, respectively, which were reduced with LiAlH4 to the dithiols Me2Si[(CH2)3SH]2 (3) and MeSi[(CH2)3SH]3 (4). This protocol was applied to the first and second generations of the doubly and triply-branched carbosilane allyl dendrimers, Si[(CH2)3SiMe(CH2CHCH2)2]4 (G(1)allyl-8), Si[(CH2)3SiMe{(CH2)3SiMe(CH2CHCH2)2}2]4 (G(2)allyl-16), Si[(CH2)3Si(CH2CHCH2)3]4 (G(1)allyl-12), and Si[(CH2)3Si{(CH2)3Si(CH2CHCH2)3}3]4 (G(2)allyl-36) to give the corresponding SH functionalised surface dendrimers Si[(CH2)3SiMe(CH2CH2CH2SH)2]4 (G(1)SH-8), G(2)SH-16, G(1)SH-12, and G(2)SH-36. Reactions of 3 with [M(acac)(diolefin)] (M = Rh, Ir; diolefin = 1,5-cyclooctadiene, 2,5-norbornadiene) gave the compounds of the type [M2(µ-Me2Si[(CH2)3S]2)(diolefin)2]n. These diolefin complexes are octanuclear (n = 4) in solution while the complex [Rh2(µ-Me2Si[(CH2)3S]2)(cod)2]n (5) is tetranuclear in the solid state. The structure of 5, solved by X-ray diffraction methods, consists of a 20-membered metallomacrocycle formed by two dimethylbis(propylthiolate)silane moieties bridging four fragments Rh(cod) in a µ2 fashion through the sulfur atoms. Treatment of [Rh(acac)(CO)2] with 3 gave [Rh2(µ-Me2Si[(CH2)3S]2)(CO)4]n, which is a mixture of tetra (n = 2) and octanuclear (n = 4) complexes in a 2 : 1 ratio in solution, while the related complex [Rh2(µ-Me2Si[(CH2)3S]2)(CO)2(PPh3)2]2 is tetranuclear. Reactions of [Rh(acac)(L–L)] (L–L = cod, (CO)2, (CO)(PPh3)) with 4 and the dendrimers G(1)SH-8, G(2)SH-16, and G(1)SH-12, gave microcrystalline solids of formulae [Rh3(MeSi[(CH2)3S]3)(L–L)3]n, [Si[(CH2)3SiMe{(CH2)3SRh(cod)}2]4]n ([G(1)Rh(cod)-8]n), [Si[(CH2)3Si{(CH2)3SRh(cod)}3]4]n ([G(1)Rh(cod)-12]n), etc., which presumably are tridimensional coordination polymers.
You have access to this article
Please wait while we load your content... Something went wrong. Try again?
Supplementary files
Article information
DOI
https://doi.org/10.1039/B504218F
Article type
Paper
Submitted
24 Mar 2005
Accepted
07 Jul 2005
First published
28 Jul 2005
Download Citation
Dalton Trans., 2005, 3092-3100
Permissions
Peripheral SH-functionalisation of carbosilane dendrimers including the synthesis of the model compound dimethylbis(propanethiol)silane and their interaction with rhodium complexes
J. A. Camerano, M. A. Casado, M. A. Ciriano, C. Tejel and L. A. Oro,Dalton Trans., 2005, 3092DOI: 10.1039/B504218F
To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.
If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.
If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.
Read more about how to correctly acknowledge RSC content.