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Aromatic PCN Palladium Pincer Complexes. Probing the Hemilability through Reactions with Nucleophiles

Fleckhaus, André LU ; Mousa, Abdelrazek LU ; Lawal, Nasir Sallau; Kiriakidou-Kazemifar, Nitsa LU and Wendt, Ola LU (2015) In Organometallics 34(9). p.1627-1634
Abstract
A series of unsymmetrical PCN pincer ligands (1-(3-((di-tert-butylphosphino)methyl)phenyl)-N,N-dialkyl-methanamine) were cyclometalated with palladium to generate a series of new PCN supported Pd(II) chloro complexes, (PCN)PdCl (4-6), where alkyl = methyl, ethyl, and n-propyl, which were fully characterized by NMR spectroscopy and X-ray crystallography. The N,N-dimethyl complex 4 reacts with methyl lithium to give the corresponding methyl and dimethyl complexes (PCN)PdMe (12) and Li[(PCN)PdMe2] (13), which could not be isolated but were characterized in solution. The substitution reactions of (PCN)PdCl (4-6) with iodide to form the corresponding iodo complexes (PCN)PdI (7-9) were investigated by Use of UV-vis stopped-flow... (More)
A series of unsymmetrical PCN pincer ligands (1-(3-((di-tert-butylphosphino)methyl)phenyl)-N,N-dialkyl-methanamine) were cyclometalated with palladium to generate a series of new PCN supported Pd(II) chloro complexes, (PCN)PdCl (4-6), where alkyl = methyl, ethyl, and n-propyl, which were fully characterized by NMR spectroscopy and X-ray crystallography. The N,N-dimethyl complex 4 reacts with methyl lithium to give the corresponding methyl and dimethyl complexes (PCN)PdMe (12) and Li[(PCN)PdMe2] (13), which could not be isolated but were characterized in solution. The substitution reactions of (PCN)PdCl (4-6) with iodide to form the corresponding iodo complexes (PCN)PdI (7-9) were investigated by Use of UV-vis stopped-flow spectrophotometry. The experiments were performed in methanol civet a temperature range from 293 to 325 K. The reactions are reversible and were shown to proceed exclusively via the solvent complex in two reversible consecutive steps. Activation parameters for both the forward and reverse reactions were determined, and they, together with reactivity trends,, support an associative pathway. No displacement of the nitrogen donor was detected, and overall this points to a limited hemilability of the ligands on palladium. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organometallics
volume
34
issue
9
pages
1627 - 1634
publisher
The American Chemical Society
external identifiers
  • wos:000354504200005
  • scopus:84929191593
ISSN
1520-6041
DOI
10.1021/om501231k
language
English
LU publication?
yes
id
05a85a1b-a6ff-4d21-9a14-c1e1a1356568 (old id 7422052)
date added to LUP
2015-06-26 14:13:30
date last changed
2017-07-30 03:14:45
@article{05a85a1b-a6ff-4d21-9a14-c1e1a1356568,
  abstract     = {A series of unsymmetrical PCN pincer ligands (1-(3-((di-tert-butylphosphino)methyl)phenyl)-N,N-dialkyl-methanamine) were cyclometalated with palladium to generate a series of new PCN supported Pd(II) chloro complexes, (PCN)PdCl (4-6), where alkyl = methyl, ethyl, and n-propyl, which were fully characterized by NMR spectroscopy and X-ray crystallography. The N,N-dimethyl complex 4 reacts with methyl lithium to give the corresponding methyl and dimethyl complexes (PCN)PdMe (12) and Li[(PCN)PdMe2] (13), which could not be isolated but were characterized in solution. The substitution reactions of (PCN)PdCl (4-6) with iodide to form the corresponding iodo complexes (PCN)PdI (7-9) were investigated by Use of UV-vis stopped-flow spectrophotometry. The experiments were performed in methanol civet a temperature range from 293 to 325 K. The reactions are reversible and were shown to proceed exclusively via the solvent complex in two reversible consecutive steps. Activation parameters for both the forward and reverse reactions were determined, and they, together with reactivity trends,, support an associative pathway. No displacement of the nitrogen donor was detected, and overall this points to a limited hemilability of the ligands on palladium.},
  author       = {Fleckhaus, André and Mousa, Abdelrazek and Lawal, Nasir Sallau and Kiriakidou-Kazemifar, Nitsa and Wendt, Ola},
  issn         = {1520-6041},
  language     = {eng},
  number       = {9},
  pages        = {1627--1634},
  publisher    = {The American Chemical Society},
  series       = {Organometallics},
  title        = {Aromatic PCN Palladium Pincer Complexes. Probing the Hemilability through Reactions with Nucleophiles},
  url          = {http://dx.doi.org/10.1021/om501231k},
  volume       = {34},
  year         = {2015},
}