חיפוש מתקדם
Organometallics
Poverenov, E., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot 76100, Israel
Leitus, G., Unit of Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel
Shimon, L.J.W., 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
A series of the first C-metalated diazoalkane complexes of Pt, based on pincer-type PCN and PCP ligands (PCP = C6)H3[CH 2P(iPr)2]2) PCN = C2H 3[CH2P(tBu)2](CH2) 2N(CH3)2), with the general formula (PCX)Pt[C(N2)R] (2, X = N, R = Ph; 3, X = N, R = SiMe3; 5, X = P, R = Ph) were prepared via direct nucleophilic attack of RCN 2 -Li+ at the metal center. These remarkably stable complexes were characterized by 1H, 31P{ 1H}, and 13C NMR and IR spectroscopy. Complex 2 was also characterized by single-crystal X-ray crystallography. Reactions of the C-metalated diazoalkane Pt complexes with Cu(I) (reported to catalyze decomposition of diazoalkanes) were strongly influenced by the nature of the pincer ligand. Bimolecular coupling to generate diphenylacetylene and (PCP)Pt-OTf (6) was observed in the case of the rigid PCP-based complex 5, while the hemilabile PCN-based complex 2 was converted to an ylide-bridged dimeric structure, the formation of which was promoted by the decoordination of the ligand amine arm. In addition, formation of the stable metalsubstituted azine-type binuclear complex 10, generated by reaction of 2 with Rh 2(OAc)4, is described. © 2005 American Chemical Society.
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תנאי שימוש
C-metalated diazoalkane complexes of platinum based on PCP- And PCN-type ligands
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Poverenov, E., Department of Organic Chemistry, Weizmann Institute of Science, Rehovot 76100, Israel
Leitus, G., Unit of Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel
Shimon, L.J.W., 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
C-metalated diazoalkane complexes of platinum based on PCP- And PCN-type ligands
A series of the first C-metalated diazoalkane complexes of Pt, based on pincer-type PCN and PCP ligands (PCP = C6)H3[CH 2P(iPr)2]2) PCN = C2H 3[CH2P(tBu)2](CH2) 2N(CH3)2), with the general formula (PCX)Pt[C(N2)R] (2, X = N, R = Ph; 3, X = N, R = SiMe3; 5, X = P, R = Ph) were prepared via direct nucleophilic attack of RCN 2 -Li+ at the metal center. These remarkably stable complexes were characterized by 1H, 31P{ 1H}, and 13C NMR and IR spectroscopy. Complex 2 was also characterized by single-crystal X-ray crystallography. Reactions of the C-metalated diazoalkane Pt complexes with Cu(I) (reported to catalyze decomposition of diazoalkanes) were strongly influenced by the nature of the pincer ligand. Bimolecular coupling to generate diphenylacetylene and (PCP)Pt-OTf (6) was observed in the case of the rigid PCP-based complex 5, while the hemilabile PCN-based complex 2 was converted to an ylide-bridged dimeric structure, the formation of which was promoted by the decoordination of the ligand amine arm. In addition, formation of the stable metalsubstituted azine-type binuclear complex 10, generated by reaction of 2 with Rh 2(OAc)4, is described. © 2005 American Chemical Society.
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