Syntheses and reactivities of indole and indolyl complexes of (cymene)ruthenium(II)

Journal Article · Wed Mar 01 04:00:00 EST 1995 · Organometallics

DOI:https://doi.org/10.1021/om00003a024· OSTI ID:28696

Chen, S; Carperos, V; Noll, B; Swope, R J; DuBois, M R ^[1]

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1. Univ. of Colorado, Boulder, CO (United States)

In this paper, we report the synthesis and characterization of related sandwich complexes of (cymene)Ru-(II) containing the indole and indolyl ligands. We wished to compare the effect of metal {pi}-coordination on the reactivities of the pyrrole and indole rings. Both indole and indolyl derivatives of (cymene)Ru-(II) have been synthesized and characterized. The {eta}{sup 6}-coordination of the carbocyclic ring of the bicyclic ligand has been confirmed by X-ray diffraction studies for both the indole and indolyl complexes. The aqueous pK{sub a} values of the coordinated indole, 2-methyl- and 2,3-dimethylindole ligands were determined to be 7.71, 8.02, and 8.15, respectively. Coordination of a second metal ion to [(cymene)Ru(2,3-dimethylindolyl)]OTf occurred at the anionic nitrogen of the pyrrolyl ring and the heteronuclear {eta}{sup 6}-{eta}{sup 1} complexes [(cymene)Ru(2,3-dimethylindolyl)PdCl{sub 2}PPh3]OTf (5) and [(cymene)Ru(2,3-dimethylindolyl)]{sub 2}Cu)(OTf){sub 3} (6) have been isolated. The coordination of the Cu(I) ion in the indolyl complex led to a pattern of nucleophilic addition for 6 similar to that observed for [(cymene)Ru(1-methylindole]{sup 2+} (3b). However, the selectivity of the reaction with 6 was significantly enhanced, and only a single regioisomer of the hydride addition product was formed at -78{degree}C. 20 refs., 4 figs., 4 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 28696
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 3 Vol. 14; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ACTIVATION ENERGY
BOND LENGTHS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
CYMENE
EXPERIMENTAL DATA
INDOLES
MOLECULAR STRUCTURE
NMR SPECTRA
NUMERICAL DATA
ORGANOMETALLIC COMPOUNDS
RUTHENIUM COMPLEXES