The University of Southampton
University of Southampton Institutional Repository

B-substituted (arene)ruthenacarborane-sulfonium, -thioether and -mercaptan complexes: mild single and double dealkylation and structural implications in the antipodal distance

B-substituted (arene)ruthenacarborane-sulfonium, -thioether and -mercaptan complexes: mild single and double dealkylation and structural implications in the antipodal distance
B-substituted (arene)ruthenacarborane-sulfonium, -thioether and -mercaptan complexes: mild single and double dealkylation and structural implications in the antipodal distance
Reactions of [RuCl2(eta(6)-arene)(2) (arene = benzene, p-cymene) with nido-[7-R-10-L-7,8-C2B9H9](-) in THF at room temperature for 3 d give the (arene)ruthenacarborane complexes closo-[3-Ru(eta(6)-arene)-l-R-8-L-l,2-C2B9H9](-) {arene = benzene, R = H [L = Me2S (1a), THT (1b), EtPhS (1c)], R = Me [L = Me2S (2a)]; arene = p-cymene, R = H [L = Me2S (3a)]} and mercaptan closo-[3-Ru(n(6)-arene)-1-R-8-HS-1,2-C2B9H9] [arene = benzene, R = H (4), Me (5); arene = p-cymene, R = H (6)] in yields of 20-40% and 22-29%, respectively. The asymmetric ligand nido-[9-Me2S-7,8-C2B9H10](-) leads to the thioether complex closo-[3-Ru(q 6 -benzene) -7-MeS- 1,2C(2)B(9)H(10)] (8) in 34 % yield under the same reaction conditions. The crystal structure of la is described and compared with those of 4 and 8. The fully assigned B-11 NMR spectroscopic data for a whole series of ruthenacarboranes having B-substituted sulfonium, thioether and mercaptan groups are presented. These data show a relation between antipodal cluster atom distances (antipodal distance) and antipodal effect (AE) in the crystal structures of these complexes and for other families of heteroboranes such as closo-[EB11H11] and closo-[EB9H9].
antipodal effect, (arene)ruthenacarboranes, carboranes, charge-compensated ligands, dealkylations bond-cleavage, sandwich ruthenium complexes, charge-compensatedligands, agostic b-h-&gt, ru bonds, nmr chemical-shifts, molecular-structure, crystal-structures, monocarbaborane chemistry, closo-heteroboranes, enhanced activity
1434-1948
4193-4205
Planas, José Giner
98b21b50-1c21-4265-bd3c-67afe28ef652
Viñas, Clara
636b5d2e-fefb-4e83-93df-9615eee8e771
Teixidor, Francesc
d24b81b5-5d82-42ca-bd30-fd9c73d0ee68
Light, Mark E.
13b5eb33-3114-4fb7-8500-90ce69e9933c
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28
Ogilvie, Helen R.
a4e15b09-9ebe-4f1f-957b-7266e4895a32
Planas, José Giner
98b21b50-1c21-4265-bd3c-67afe28ef652
Viñas, Clara
636b5d2e-fefb-4e83-93df-9615eee8e771
Teixidor, Francesc
d24b81b5-5d82-42ca-bd30-fd9c73d0ee68
Light, Mark E.
13b5eb33-3114-4fb7-8500-90ce69e9933c
Hursthouse, Michael B.
a65b4d35-2ea0-47e7-938a-d744f4d9ba28
Ogilvie, Helen R.
a4e15b09-9ebe-4f1f-957b-7266e4895a32

Planas, José Giner, Viñas, Clara, Teixidor, Francesc, Light, Mark E., Hursthouse, Michael B. and Ogilvie, Helen R. (2005) B-substituted (arene)ruthenacarborane-sulfonium, -thioether and -mercaptan complexes: mild single and double dealkylation and structural implications in the antipodal distance. European Journal of Inorganic Chemistry, (20), 4193-4205. (doi:10.1002/ejic.200500470).

Record type: Article

Abstract

Reactions of [RuCl2(eta(6)-arene)(2) (arene = benzene, p-cymene) with nido-[7-R-10-L-7,8-C2B9H9](-) in THF at room temperature for 3 d give the (arene)ruthenacarborane complexes closo-[3-Ru(eta(6)-arene)-l-R-8-L-l,2-C2B9H9](-) {arene = benzene, R = H [L = Me2S (1a), THT (1b), EtPhS (1c)], R = Me [L = Me2S (2a)]; arene = p-cymene, R = H [L = Me2S (3a)]} and mercaptan closo-[3-Ru(n(6)-arene)-1-R-8-HS-1,2-C2B9H9] [arene = benzene, R = H (4), Me (5); arene = p-cymene, R = H (6)] in yields of 20-40% and 22-29%, respectively. The asymmetric ligand nido-[9-Me2S-7,8-C2B9H10](-) leads to the thioether complex closo-[3-Ru(q 6 -benzene) -7-MeS- 1,2C(2)B(9)H(10)] (8) in 34 % yield under the same reaction conditions. The crystal structure of la is described and compared with those of 4 and 8. The fully assigned B-11 NMR spectroscopic data for a whole series of ruthenacarboranes having B-substituted sulfonium, thioether and mercaptan groups are presented. These data show a relation between antipodal cluster atom distances (antipodal distance) and antipodal effect (AE) in the crystal structures of these complexes and for other families of heteroboranes such as closo-[EB11H11] and closo-[EB9H9].

Full text not available from this repository.

More information

Published date: 21 October 2005
Keywords: antipodal effect, (arene)ruthenacarboranes, carboranes, charge-compensated ligands, dealkylations bond-cleavage, sandwich ruthenium complexes, charge-compensatedligands, agostic b-h-&gt, ru bonds, nmr chemical-shifts, molecular-structure, crystal-structures, monocarbaborane chemistry, closo-heteroboranes, enhanced activity

Identifiers

Local EPrints ID: 20888
URI: http://eprints.soton.ac.uk/id/eprint/20888
ISSN: 1434-1948
PURE UUID: 9a0de753-a2cf-476d-8070-b3373352f61e

Catalogue record

Date deposited: 02 Mar 2006
Last modified: 15 Jul 2019 19:25

Export record

Altmetrics

Contributors

Author: José Giner Planas
Author: Clara Viñas
Author: Francesc Teixidor
Author: Mark E. Light
Author: Michael B. Hursthouse
Author: Helen R. Ogilvie

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×