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Aliphatic pincer-type POCOP ligands and their complexation behaviour with iridium: Crystal structure of an iridium(III) phosphinite complex

Jonasson, Klara LU ; Ahlsten, Nanna and Wendt, Ola LU (2011) In Inorganica Chimica Acta 379(1). p.76-80
Abstract
Reaction of 2 equivalents of 1,3-bis-(di-tert-butylphosphinito)-2-methyl-propane (1a) with [Ir(COD)Cl](2) affords the first aliphatic diphosphinite PCP pincer complex with iridium, Ir(H){(t-Bu2POCH2)(2)C(Me)}Cl (2). The poor yield of 2 is partly explained by the formation of a di-nuclear byproduct [IrCl(COD)](2)(mu(2)-{(t-Bu2POCH2)(2)CH(Me)}) (3). Reaction of 1,3-bis-(di-iso-propylphosphinito)-2-methyl-propane (1b) under the same condition does not give any cyclometallation, and reaction with IrCl3 center dot H2O in DMF leads to complete decomposition of the pincer ligand under the formation of Ir(H)(i-Pr2P(OH))(3)(CO) (4), underpinning the comparatively low thermal stability of aliphatic phosphinite pincer systems. (C) 2011 Elsevier B.V.... (More)
Reaction of 2 equivalents of 1,3-bis-(di-tert-butylphosphinito)-2-methyl-propane (1a) with [Ir(COD)Cl](2) affords the first aliphatic diphosphinite PCP pincer complex with iridium, Ir(H){(t-Bu2POCH2)(2)C(Me)}Cl (2). The poor yield of 2 is partly explained by the formation of a di-nuclear byproduct [IrCl(COD)](2)(mu(2)-{(t-Bu2POCH2)(2)CH(Me)}) (3). Reaction of 1,3-bis-(di-iso-propylphosphinito)-2-methyl-propane (1b) under the same condition does not give any cyclometallation, and reaction with IrCl3 center dot H2O in DMF leads to complete decomposition of the pincer ligand under the formation of Ir(H)(i-Pr2P(OH))(3)(CO) (4), underpinning the comparatively low thermal stability of aliphatic phosphinite pincer systems. (C) 2011 Elsevier B.V. All rights reserved. (Less)
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organization
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Contribution to journal
publication status
published
subject
keywords
Aliphatic pincer complexes, Cyclometallation, Iridium, Phosphinites
in
Inorganica Chimica Acta
volume
379
issue
1
pages
76 - 80
publisher
Elsevier
external identifiers
  • wos:000297266200012
  • scopus:81755165854
ISSN
0020-1693
DOI
10.1016/j.ica.2011.09.034
language
English
LU publication?
yes
id
433668aa-fcae-49e6-8ba9-25de6fc0cbf7 (old id 2272086)
date added to LUP
2011-12-29 13:58:16
date last changed
2017-10-22 04:14:11
@article{433668aa-fcae-49e6-8ba9-25de6fc0cbf7,
  abstract     = {Reaction of 2 equivalents of 1,3-bis-(di-tert-butylphosphinito)-2-methyl-propane (1a) with [Ir(COD)Cl](2) affords the first aliphatic diphosphinite PCP pincer complex with iridium, Ir(H){(t-Bu2POCH2)(2)C(Me)}Cl (2). The poor yield of 2 is partly explained by the formation of a di-nuclear byproduct [IrCl(COD)](2)(mu(2)-{(t-Bu2POCH2)(2)CH(Me)}) (3). Reaction of 1,3-bis-(di-iso-propylphosphinito)-2-methyl-propane (1b) under the same condition does not give any cyclometallation, and reaction with IrCl3 center dot H2O in DMF leads to complete decomposition of the pincer ligand under the formation of Ir(H)(i-Pr2P(OH))(3)(CO) (4), underpinning the comparatively low thermal stability of aliphatic phosphinite pincer systems. (C) 2011 Elsevier B.V. All rights reserved.},
  author       = {Jonasson, Klara and Ahlsten, Nanna and Wendt, Ola},
  issn         = {0020-1693},
  keyword      = {Aliphatic pincer complexes,Cyclometallation,Iridium,Phosphinites},
  language     = {eng},
  number       = {1},
  pages        = {76--80},
  publisher    = {Elsevier},
  series       = {Inorganica Chimica Acta},
  title        = {Aliphatic pincer-type POCOP ligands and their complexation behaviour with iridium: Crystal structure of an iridium(III) phosphinite complex},
  url          = {http://dx.doi.org/10.1016/j.ica.2011.09.034},
  volume       = {379},
  year         = {2011},
}