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)
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
2006
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), .
(doi:10.1039/b605198g).
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.
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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: http://eprints.soton.ac.uk/id/eprint/44397
ISSN: 1477-9226
PURE UUID: 8df22d2c-fdcd-4fce-a212-3a090f46c0f8
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Date deposited: 01 Mar 2007
Last modified: 16 Mar 2024 02:43
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Author:
Michael D. Brown
Author:
Michael Webster
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