The University of Southampton
University of Southampton Institutional Repository

Preparation and properties of cyclic and open-chain Sb/N-donor ligands

Preparation and properties of cyclic and open-chain Sb/N-donor ligands
Preparation and properties of cyclic and open-chain Sb/N-donor ligands
The preparations of both open-chain and cyclic mixed-donor Sb/N ligands, MeN(CH2-2-C6H4)2SbMe (1), MeN(CH2-2-C6H4SbMe2)2 (2), CH2{CH2N(Me)CH2-2-C6H4SbMe2}2 (3) and CH2{CH2N(Me)CH2-2-C6H4}2SbMe (4), are described via reaction of chlorostibines with dilithio-reagents, and their spectroscopic properties established. Air-stable stibonium derivatives of (3) and (4) have been isolated by treatment of the compounds with excess MeI, which leads to quaternisation at the Sb atoms exclusively. A crystal structure of a bis(stibonium) derivative of (3), [CH2{CH2N(Me)CH2-2-C6H4SbMe3}2]I2, reveals hypervalency at Sb through long-range Sb...N interactions (ca. 2.87 A), giving pseudo-five-membered rings fused to the aromatic rings, and distorted trigonal bipyramidal coordination at Sb. The coordinating properties of compounds (1) to (4) have been investigated through their reactions with Cu(I), Mn(I), Mo(0) and Pt(IV) reagents, and for (1) and (4) by reaction with Fe(0), giving [Fe(CO)4(L)]. The spectroscopic data (IR, 1H, 13C{1H}, 55Mn, 63Cu, 95Mo and 195Pt NMR), mass spectrometry and microanalyses for this series of complexes confirm that coordination occurs via the Sb donor atoms in all cases, with N-coordination only present in fac-[Mn(CO)3(2)](CF3SO3). Crystal structures of [Cu(2)2]BF4, [Mo(CO)4(2)] and [PtMe3I(2)] confirm the coordination modes, showing (2) functioning as a wide-angle bidentate distibine. The structures also show the amine N-donor atoms in the complexes are involved in a hypervalent SbN interaction (ca. 3.0 A) with one of the coordinated Sb atoms in each ligand, leading to significant differences in the conformations of the carbon backbones linking the Sb and N atoms. Reaction of Na3[RhCl6].12H2O with one mol equiv. of (2), (3) or (4) leads to the bis-ligand complex [RhCl2(2)2]Cl and the 1 : 1 Rh : L complexes [RhCl2(3)]Cl and [RhCl3(4)], both of which involve coordination via the Sb and N donor atoms.

0300-9246
7811-7819
Jura, Marek
e4a8ae2b-5609-45bb-99d8-a2320b9c89b9
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Jura, Marek
e4a8ae2b-5609-45bb-99d8-a2320b9c89b9
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Jura, Marek, Levason, William, Reid, Gillian and Webster, Michael (2009) Preparation and properties of cyclic and open-chain Sb/N-donor ligands. Dalton Transactions, 37, 7811-7819. (doi:10.1039/b909226a).

Record type: Article

Abstract

The preparations of both open-chain and cyclic mixed-donor Sb/N ligands, MeN(CH2-2-C6H4)2SbMe (1), MeN(CH2-2-C6H4SbMe2)2 (2), CH2{CH2N(Me)CH2-2-C6H4SbMe2}2 (3) and CH2{CH2N(Me)CH2-2-C6H4}2SbMe (4), are described via reaction of chlorostibines with dilithio-reagents, and their spectroscopic properties established. Air-stable stibonium derivatives of (3) and (4) have been isolated by treatment of the compounds with excess MeI, which leads to quaternisation at the Sb atoms exclusively. A crystal structure of a bis(stibonium) derivative of (3), [CH2{CH2N(Me)CH2-2-C6H4SbMe3}2]I2, reveals hypervalency at Sb through long-range Sb...N interactions (ca. 2.87 A), giving pseudo-five-membered rings fused to the aromatic rings, and distorted trigonal bipyramidal coordination at Sb. The coordinating properties of compounds (1) to (4) have been investigated through their reactions with Cu(I), Mn(I), Mo(0) and Pt(IV) reagents, and for (1) and (4) by reaction with Fe(0), giving [Fe(CO)4(L)]. The spectroscopic data (IR, 1H, 13C{1H}, 55Mn, 63Cu, 95Mo and 195Pt NMR), mass spectrometry and microanalyses for this series of complexes confirm that coordination occurs via the Sb donor atoms in all cases, with N-coordination only present in fac-[Mn(CO)3(2)](CF3SO3). Crystal structures of [Cu(2)2]BF4, [Mo(CO)4(2)] and [PtMe3I(2)] confirm the coordination modes, showing (2) functioning as a wide-angle bidentate distibine. The structures also show the amine N-donor atoms in the complexes are involved in a hypervalent SbN interaction (ca. 3.0 A) with one of the coordinated Sb atoms in each ligand, leading to significant differences in the conformations of the carbon backbones linking the Sb and N atoms. Reaction of Na3[RhCl6].12H2O with one mol equiv. of (2), (3) or (4) leads to the bis-ligand complex [RhCl2(2)2]Cl and the 1 : 1 Rh : L complexes [RhCl2(3)]Cl and [RhCl3(4)], both of which involve coordination via the Sb and N donor atoms.

Full text not available from this repository.

More information

Published date: 7 October 2009

Identifiers

Local EPrints ID: 146941
URI: http://eprints.soton.ac.uk/id/eprint/146941
ISSN: 0300-9246
PURE UUID: f8b74e39-7aa5-4fb2-a77c-d5422245e562
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 22 Apr 2010 15:34
Last modified: 20 Jul 2019 01:28

Export record

Altmetrics

Contributors

Author: Marek Jura
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD
Author: Michael Webster

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.

×