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פותח על ידי קלירמאש פתרונות בע"מ -
Pincer "hemilabile" effect. PCN platinum(II) complexes with different amine "arm length"
Year:
2005
Source of publication :
Organometallics
Authors :
פוברנוב, ילנה
;
.
Volume :
24
Co-Authors:
Poverenov, E., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Gandelman, M., 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
Rozenberg, H., Unit of Chemical Research Support, Weizmann Institute of Science, Rehovot, 76100, Israel
Ben-David, Y., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Milstein, D., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Facilitators :
From page:
1082
To page:
1090
(
Total pages:
9
)
Abstract:
The reactivity of the "long arm" PCN-type pincer ligand C 6H4[CH2P(tBu)2](CH2) 2N(CH3)2 (1), which forms complexes bearing a six-member ed amine chelate and a five-membered phosphine chelate, was compared with that of the new "normal" PCN ligand C6H 4[CH2P-(tBu)2](CH2)N(CH 2CH3)2 (2), which leads to formation of complexes bearing two five-membered chelates. The chloride complexes (PCN)PtCl (3, 4) and the unsaturated cationic complexes [(PCN)Pt]+X- (X = BF4, OTf) (5,6,7), based on both PCN ligands, were prepared and reacted with different reagents to give aqua, [(PCN-1)Pt(H2O)] +BF4 - (10); hydroxo, (PCN-1)Pt(OH) (11); carbonyl [(PCN)Pt(CO)]+BF4 - (8, 9); and hydride, (PCN-1)PtH (16) complexes. The structures of complexes 4, 6, 8, 10, 11, and 12 were determined by X-ray crystallography. When both carbonyl complexes were treated with hydrogen gas, the "long arm" PCN-1-based complex 8 led to formation of a trimeric cluster, [C6H6[CH 2P(tBu)2]-(CH2)2N(CH 3)2Pt(CO)]3 (12), while the "normal" PCN-based complex 9 remained unchanged under the same conditions. This observation clearly demonstrates the very significant effect of the amine arm length (five- vs six-membered chelate) on the hemilability of the ligand and the reactivity of the corresponding complexes. © 2005 American Chemical Society.
Note:
Related Files :
Alcohols
Amines
Carbonyl complexes
catalysis
Organic acids
Organometallics
X ray crystallography
עוד תגיות
תוכן קשור
More details
DOI :
10.1021/om049182m
Article number:
Affiliations:
Database:
סקופוס
Publication Type:
מאמר
;
.
Language:
אנגלית
Editors' remarks:
ID:
26060
Last updated date:
02/03/2022 17:27
Creation date:
17/04/2018 00:19
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Scientific Publication
Pincer "hemilabile" effect. PCN platinum(II) complexes with different amine "arm length"
24
Poverenov, E., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Gandelman, M., 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
Rozenberg, H., Unit of Chemical Research Support, Weizmann Institute of Science, Rehovot, 76100, Israel
Ben-David, Y., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Milstein, D., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel
Pincer "hemilabile" effect. PCN platinum(II) complexes with different amine "arm length"
The reactivity of the "long arm" PCN-type pincer ligand C 6H4[CH2P(tBu)2](CH2) 2N(CH3)2 (1), which forms complexes bearing a six-member ed amine chelate and a five-membered phosphine chelate, was compared with that of the new "normal" PCN ligand C6H 4[CH2P-(tBu)2](CH2)N(CH 2CH3)2 (2), which leads to formation of complexes bearing two five-membered chelates. The chloride complexes (PCN)PtCl (3, 4) and the unsaturated cationic complexes [(PCN)Pt]+X- (X = BF4, OTf) (5,6,7), based on both PCN ligands, were prepared and reacted with different reagents to give aqua, [(PCN-1)Pt(H2O)] +BF4 - (10); hydroxo, (PCN-1)Pt(OH) (11); carbonyl [(PCN)Pt(CO)]+BF4 - (8, 9); and hydride, (PCN-1)PtH (16) complexes. The structures of complexes 4, 6, 8, 10, 11, and 12 were determined by X-ray crystallography. When both carbonyl complexes were treated with hydrogen gas, the "long arm" PCN-1-based complex 8 led to formation of a trimeric cluster, [C6H6[CH 2P(tBu)2]-(CH2)2N(CH 3)2Pt(CO)]3 (12), while the "normal" PCN-based complex 9 remained unchanged under the same conditions. This observation clearly demonstrates the very significant effect of the amine arm length (five- vs six-membered chelate) on the hemilability of the ligand and the reactivity of the corresponding complexes. © 2005 American Chemical Society.
Scientific Publication
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