The University of Southampton
University of Southampton Institutional Repository

Synthesis and properties of Rh(I) and Ir(I) distibine complexes with organometallic co-ligands

Synthesis and properties of Rh(I) and Ir(I) distibine complexes with organometallic co-ligands
Synthesis and properties of Rh(I) and Ir(I) distibine complexes with organometallic co-ligands
The first series of Rh(I) distibine complexes with organometallic co-ligands is described, including the five-coordinate [Rh(cod)(distibine)Cl], the 16-electron planar cations [Rh(cod)(distibine)] BF4 and [Rh{Ph2Sb(CH2)(3)SbPh2}(2)] BF4 and the five-coordinate [Rh(CO)(distibine)(2)][Rh(CO)(2)Cl-2] (distibine = R2Sb(CH2)(3)SbR2, R = Ph or Me, and o-C6H4(CH2SbMe2)(2)). The corresponding Ir(I) species [Ir( cod)(distibine)] BF4 and [Ir{Ph2Sb(CH2)(3)SbPh2}2] BF4 have also been prepared. The complexes have been characterised by H-1 and C-13{H-1} NMR and IR spectroscopy, electrospray mass spectrometry and microanalysis. The crystal structure of the anion exchanged [Rh(CO){Ph2Sb(CH2)(3)SbPh2}(2)]PF6 center dot 3/4CH(2)Cl(2) is also described. The methyl-substituted distibine complexes are less stable than the complexes of Ph2Sb(CH2)(3)SbPh2, with C-Sb fission occurring in some of the complexes of the former. The salts [Rh(CO){Ph2Sb(CH2)(3)SbPh2}(2)]PF6 and [Rh{Ph2Sb(CH2)(3)SbPh2}2] BF4 undergo oxidative addition with Br-2 to give the known [RhBr2{Ph2Sb(CH2)(3)SbPh2}(2)](+), while using HCl gives the same hydride complex from both precursors, which is tentatively assigned as [RhHCl2{Ph2Sb(CH2)(3)SbPh2}]. An unexpected further Rh(III) product from this reaction, trans-[RhCl2{Ph2Sb(CH2)(3)SbPh2}{PhClSb(CH2)(3)SbClPh}]Cl, was identified by a crystal structure analysis and represents the first structurally characterised example of a chlorostibine coordinated to a metal. [Rh{Ph2Sb(CH2)(3)SbPh2}(2)] BF4 reacts with CO to give [Rh(CO){Ph2Sb(CH2)(3)SbPh2}(2)]BF4 initially, and upon further exposure this species undergoes further reversible carbonylation to give a cis-dicarbonyl species thought to be [Rh(CO)(2){Ph2Sb(CH2)(3)SbPh2}{kappa Sb-1-Ph2Sb(CH2)(3)SbPh2}]BF4 which converts back to the monocarbonyl complex when the CO atmosphere is replaced with N-2.
ray crystal-structure, coordination chemistry, iridium(iii) complexes, rh(sbph3)(3)(co)x x, molecular-structure, propargyl compounds, stibine complexes, halide-complexes, metal center, rhodium(i)
1477-9226
4039-4046
Brown, Michael D.
76a42341-1a1e-4ec9-8cdc-aca9d5e53bf4
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Brown, Michael D.
76a42341-1a1e-4ec9-8cdc-aca9d5e53bf4
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Brown, Michael D., Levason, William, Reid, Gillian and Webster, Michael (2006) Synthesis and properties of Rh(I) and Ir(I) distibine complexes with organometallic co-ligands. Dalton Transactions, (33), 4039-4046. (doi:10.1039/b605198g).

Record type: Article

Abstract

The first series of Rh(I) distibine complexes with organometallic co-ligands is described, including the five-coordinate [Rh(cod)(distibine)Cl], the 16-electron planar cations [Rh(cod)(distibine)] BF4 and [Rh{Ph2Sb(CH2)(3)SbPh2}(2)] BF4 and the five-coordinate [Rh(CO)(distibine)(2)][Rh(CO)(2)Cl-2] (distibine = R2Sb(CH2)(3)SbR2, R = Ph or Me, and o-C6H4(CH2SbMe2)(2)). The corresponding Ir(I) species [Ir( cod)(distibine)] BF4 and [Ir{Ph2Sb(CH2)(3)SbPh2}2] BF4 have also been prepared. The complexes have been characterised by H-1 and C-13{H-1} NMR and IR spectroscopy, electrospray mass spectrometry and microanalysis. The crystal structure of the anion exchanged [Rh(CO){Ph2Sb(CH2)(3)SbPh2}(2)]PF6 center dot 3/4CH(2)Cl(2) is also described. The methyl-substituted distibine complexes are less stable than the complexes of Ph2Sb(CH2)(3)SbPh2, with C-Sb fission occurring in some of the complexes of the former. The salts [Rh(CO){Ph2Sb(CH2)(3)SbPh2}(2)]PF6 and [Rh{Ph2Sb(CH2)(3)SbPh2}2] BF4 undergo oxidative addition with Br-2 to give the known [RhBr2{Ph2Sb(CH2)(3)SbPh2}(2)](+), while using HCl gives the same hydride complex from both precursors, which is tentatively assigned as [RhHCl2{Ph2Sb(CH2)(3)SbPh2}]. An unexpected further Rh(III) product from this reaction, trans-[RhCl2{Ph2Sb(CH2)(3)SbPh2}{PhClSb(CH2)(3)SbClPh}]Cl, was identified by a crystal structure analysis and represents the first structurally characterised example of a chlorostibine coordinated to a metal. [Rh{Ph2Sb(CH2)(3)SbPh2}(2)] BF4 reacts with CO to give [Rh(CO){Ph2Sb(CH2)(3)SbPh2}(2)]BF4 initially, and upon further exposure this species undergoes further reversible carbonylation to give a cis-dicarbonyl species thought to be [Rh(CO)(2){Ph2Sb(CH2)(3)SbPh2}{kappa Sb-1-Ph2Sb(CH2)(3)SbPh2}]BF4 which converts back to the monocarbonyl complex when the CO atmosphere is replaced with N-2.

Full text not available from this repository.

More information

Published date: 2006
Keywords: ray crystal-structure, coordination chemistry, iridium(iii) complexes, rh(sbph3)(3)(co)x x, molecular-structure, propargyl compounds, stibine complexes, halide-complexes, metal center, rhodium(i)

Identifiers

Local EPrints ID: 44397
URI: https://eprints.soton.ac.uk/id/eprint/44397
ISSN: 1477-9226
PURE UUID: 8df22d2c-fdcd-4fce-a212-3a090f46c0f8
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: 01 Mar 2007
Last modified: 14 Mar 2019 01:56

Export record

Altmetrics

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 https://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.

×