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PC(sp(3))P pincer carbonyl complexes of iridium(I), and iridium(III)

Jonasson, Klara LU ; Polukeev, Alexey LU and Wendt, Ola LU (2015) In RSC Advances 5(20). p.15534-15538
Abstract
The previously reported complex trans-[IrHCl{cis-1,3-bis-(di-tert-butylphosphino)methyl} cyclohexane] (2) forms the 18-electron carbonyl compound anti-[Ir(CO)HCl{cis-1,3-bis-((di-tert-butylphosphino)methyl)} cyclohexane] (5a)upon reaction with 1 atm CO. The structural isomer syn-[IrH(CO)Cl{cis-1,3-bis-((di-tert- butylphosphino)methyl)}cyclohexane] (5b)is obtained directly upon complexation of the ligand (1) with IrCl3 center dot H2O in refluxing DMF syn-5b is the first iridium aliphatic pincer complex with this orientation of the hydrogens and is the thermodynamically more stable isomer. Both compounds 5a and 5b afford the Ir(I)complex trans-[Ir(CO){cis-1,3-bis-((di-tert-butylphosphino)methyl)}cyclohexane] (4)upon treatment with KO'Bu.... (More)
The previously reported complex trans-[IrHCl{cis-1,3-bis-(di-tert-butylphosphino)methyl} cyclohexane] (2) forms the 18-electron carbonyl compound anti-[Ir(CO)HCl{cis-1,3-bis-((di-tert-butylphosphino)methyl)} cyclohexane] (5a)upon reaction with 1 atm CO. The structural isomer syn-[IrH(CO)Cl{cis-1,3-bis-((di-tert- butylphosphino)methyl)}cyclohexane] (5b)is obtained directly upon complexation of the ligand (1) with IrCl3 center dot H2O in refluxing DMF syn-5b is the first iridium aliphatic pincer complex with this orientation of the hydrogens and is the thermodynamically more stable isomer. Both compounds 5a and 5b afford the Ir(I)complex trans-[Ir(CO){cis-1,3-bis-((di-tert-butylphosphino)methyl)}cyclohexane] (4)upon treatment with KO'Bu. Complex 4 was also synthesised in a more straightforward fashion from the previously known terminal nitrogen complex trans-[Ir(N-2){cis-1,3-bis-((di-tert-butylphosphino)-methyl)} cyclohexane] (3)under atmospheric CO. The complexes 4, 5a and 5b were characterised spectroscopically and in the solid state. IR data point to a more electron rich metal centre as compared to the corresponding aromatic complexes. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
RSC Advances
volume
5
issue
20
pages
15534 - 15538
publisher
Royal Society of Chemistry
external identifiers
  • wos:000349435000072
  • scopus:84922511238
ISSN
2046-2069
DOI
10.1039/c4ra15562a
language
English
LU publication?
yes
id
1b9638df-4541-4f2f-b1c1-c975a0a3d350 (old id 5180109)
date added to LUP
2015-03-31 07:56:19
date last changed
2017-04-30 10:40:40
@article{1b9638df-4541-4f2f-b1c1-c975a0a3d350,
  abstract     = {The previously reported complex trans-[IrHCl{cis-1,3-bis-(di-tert-butylphosphino)methyl} cyclohexane] (2) forms the 18-electron carbonyl compound anti-[Ir(CO)HCl{cis-1,3-bis-((di-tert-butylphosphino)methyl)} cyclohexane] (5a)upon reaction with 1 atm CO. The structural isomer syn-[IrH(CO)Cl{cis-1,3-bis-((di-tert- butylphosphino)methyl)}cyclohexane] (5b)is obtained directly upon complexation of the ligand (1) with IrCl3 center dot H2O in refluxing DMF syn-5b is the first iridium aliphatic pincer complex with this orientation of the hydrogens and is the thermodynamically more stable isomer. Both compounds 5a and 5b afford the Ir(I)complex trans-[Ir(CO){cis-1,3-bis-((di-tert-butylphosphino)methyl)}cyclohexane] (4)upon treatment with KO'Bu. Complex 4 was also synthesised in a more straightforward fashion from the previously known terminal nitrogen complex trans-[Ir(N-2){cis-1,3-bis-((di-tert-butylphosphino)-methyl)} cyclohexane] (3)under atmospheric CO. The complexes 4, 5a and 5b were characterised spectroscopically and in the solid state. IR data point to a more electron rich metal centre as compared to the corresponding aromatic complexes.},
  author       = {Jonasson, Klara and Polukeev, Alexey and Wendt, Ola},
  issn         = {2046-2069},
  language     = {eng},
  number       = {20},
  pages        = {15534--15538},
  publisher    = {Royal Society of Chemistry},
  series       = {RSC Advances},
  title        = {PC(sp(3))P pincer carbonyl complexes of iridium(I), and iridium(III)},
  url          = {http://dx.doi.org/10.1039/c4ra15562a},
  volume       = {5},
  year         = {2015},
}