Reactive indolyl complexes of group 9 metals

Ho, Joanne Hui Hui, Black, David St Clair, Messerle, Barbara Ann, Clegg, Jack Kay and Turner, Peter (2006) Reactive indolyl complexes of group 9 metals. Organometallics, 25 24: 5800-5810. doi:10.1021/om060591n


Author Ho, Joanne Hui Hui
Black, David St Clair
Messerle, Barbara Ann
Clegg, Jack Kay
Turner, Peter
Title Reactive indolyl complexes of group 9 metals
Journal name Organometallics   Check publisher's open access policy
ISSN 0276-7333
1520-6041
Publication date 2006-11
Sub-type Article (original research)
DOI 10.1021/om060591n
Volume 25
Issue 24
Start page 5800
End page 5810
Total pages 11
Place of publication Washington, DC United States
Publisher American Chemical Society
Collection year 2006
Language eng
Formatted abstract
A series of novel indolyl-imine ligand precursors have been synthesized. In particular, bidentate, tridentate, and potentially tetradentate ligands were prepared, each containing both indolyl sp2-N and imine sp2-N donors. A series of neutral rhodium(I) and iridium(I) complexes of these ligands were synthesized, including monometallic and bimetallic complexes. The X-ray structures of three of the monometallic complexes with bidentate indolyl-imine ligands were determined. In each complex, the metal center was in a square planar conformation, as expected for Rh(I) and Ir(I) complexes. The fiveand six-membered metallocycles formed on complexation of the metal with the ligands were all planar, and the aromaticity of the ligands was maintained. The Rh(I) complex with the tridentate indolyl ligand (L) reacted at room temperature with CH2Cl2 to form the Rh(III) chloromethyl complex [Rh(L)(CO)-
(CH2Cl)(Cl)] via oxidative addition of the C-Cl bond of CH2Cl2. The Rh/Ir(I) indolyl-imine complexes are efficient catalysts for the intramolecular cyclization of 4-pentynoic acid to form ç-methylene-ç-butyrolactone. A dinuclear Rh(I) complex was the most active catalyst, demonstrating a significant degree of bimetallic cooperativity.
Keyword N-Heterocyclic Carbene
X-Ray Analyses
Rhodium(i) Complexes
Oxidative Addition
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Chemistry and Molecular Biosciences
 
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