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Cationic, neutral, and anionic platinum(II) complexes based on an electron-rich PNN ligand. New modes of reactivity based on pincer hemilability and dearomatization
Year:
2008
Source of publication :
Organometallics
Authors :
Poverenov, Elena
;
.
Volume :
27
Co-Authors:
Vuzman, D., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Poverenov, E., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Shimon, L.J.W., Unit of Chemical Research Support, Weizmann Institute of Science, Rehovot, 76100, Israel
Diskin-Posner, Y., Unit of Chemical Research Support, Weizmann Institute of Science, Rehovot, 76100, Israel
Milstein, D., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Facilitators :
From page:
2627
To page:
2634
(
Total pages:
8
)
Abstract:
The synthesis and reactivity of new Pt(II) complexes, including anionic d8 complexes, based on the electron-rich, hemilabile PNN-type pincer ligand C5H3N-2-(CH2PtBu 2)(CH2NEt2) are described. Formation of these complexes involves dearomatization/aromatization processes of the ligand. The chloride complex [(PNN)PtCl]+Cl- (1) was prepared and reacted with the base tBuOK to give the deprotonated, neutral chloride complex (PNN*)PtCl (2) (PNN* = C5H 3N-2-(CHPtBu2)(CH2NEt2)). Reaction of 2 with nBuLi gave the corresponding neutral hydride complex (PNN*)PtH (3), which was readily protonated by triflic acid to give the cationic hydride complex [(PNN)PtH]+OTf- (4). Unexpectedly, reaction of complex 2 with 1 equiv of RLi resulted in opening of the chelate ring, to give the corresponding anionic, dearomatized complexes Li+[(PNN*)Pt(Cl)(R)]- (R = methyl, 5; phenyl, 6). Notably, these complexes are relatively stable although they bear no stabilizing π acceptors that can lower the electron density at the metal center. Complexes 5 and 6 readily undergo protonation by HCl to form the corresponding neutral, aromatic complexes (PNN)Pt(Cl)(R) (R = methyl, 7; phenyl, 8), in which the hemilabile amine "arm" remains decoordinated and does not undergo protonation. Minor amounts of the dearomatized chloride complex 2 are also formed as a result of elimination of RH. Reaction of complexes 5 and 6 with water results in selective protonation-aromatization to give the corresponding complexes 7 and 8. © 2008 American Chemical Society.
Note:
Related Files :
Dearomatization
Dyes
Hemilability
New modes
Platinum(II) complexes
Platinum compounds
Reactivity (Chemical)
Synthesis (of chiral ionic liquids)
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More details
DOI :
10.1021/om8001069
Article number:
Affiliations:
Database:
Scopus
Publication Type:
article
;
.
Language:
English
Editors' remarks:
ID:
30255
Last updated date:
02/03/2022 17:27
Creation date:
17/04/2018 00:53
Scientific Publication
Cationic, neutral, and anionic platinum(II) complexes based on an electron-rich PNN ligand. New modes of reactivity based on pincer hemilability and dearomatization
27
Vuzman, D., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Poverenov, E., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Shimon, L.J.W., Unit of Chemical Research Support, Weizmann Institute of Science, Rehovot, 76100, Israel
Diskin-Posner, Y., Unit of Chemical Research Support, Weizmann Institute of Science, Rehovot, 76100, Israel
Milstein, D., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Cationic, neutral, and anionic platinum(II) complexes based on an electron-rich PNN ligand. New modes of reactivity based on pincer hemilability and dearomatization
The synthesis and reactivity of new Pt(II) complexes, including anionic d8 complexes, based on the electron-rich, hemilabile PNN-type pincer ligand C5H3N-2-(CH2PtBu 2)(CH2NEt2) are described. Formation of these complexes involves dearomatization/aromatization processes of the ligand. The chloride complex [(PNN)PtCl]+Cl- (1) was prepared and reacted with the base tBuOK to give the deprotonated, neutral chloride complex (PNN*)PtCl (2) (PNN* = C5H 3N-2-(CHPtBu2)(CH2NEt2)). Reaction of 2 with nBuLi gave the corresponding neutral hydride complex (PNN*)PtH (3), which was readily protonated by triflic acid to give the cationic hydride complex [(PNN)PtH]+OTf- (4). Unexpectedly, reaction of complex 2 with 1 equiv of RLi resulted in opening of the chelate ring, to give the corresponding anionic, dearomatized complexes Li+[(PNN*)Pt(Cl)(R)]- (R = methyl, 5; phenyl, 6). Notably, these complexes are relatively stable although they bear no stabilizing π acceptors that can lower the electron density at the metal center. Complexes 5 and 6 readily undergo protonation by HCl to form the corresponding neutral, aromatic complexes (PNN)Pt(Cl)(R) (R = methyl, 7; phenyl, 8), in which the hemilabile amine "arm" remains decoordinated and does not undergo protonation. Minor amounts of the dearomatized chloride complex 2 are also formed as a result of elimination of RH. Reaction of complexes 5 and 6 with water results in selective protonation-aromatization to give the corresponding complexes 7 and 8. © 2008 American Chemical Society.
Scientific Publication
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