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Title: Studies on the bonding of polynuclear heteroaromatic nitrogen ligands to (pentamethylcyclopentadienyl)rhodium dication: the role of nitrogen versus /pi/-complexation on the regioselective hydrogenation of the nitrogen ring

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00100a035· OSTI ID:6048282
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The reactions of quinoline (1), isoquinoline (2), 1,2,3,4-tetrahydroquinoline (3), and 2-methylquinoline (4) with (pentamethylcyclopentadienyl)rhodium dication (Cp*Rh(acetone)/sub 3//sup 2+/, Cp*Rh(acetonitrile)/sub 3//sup 2+/, or Cr*Rh(p-xylene)/sup 2+/X/sub 2/; X = PF/sub 6/ or BF/sub 4/) were studied to ascertain nitrogen (N) versus /pi/-bonding. Ligands 1 and 2 were found to form N-bonded rhodium complexes, while ligand 3 preferred /pi/-coordination (/eta//sup 6/). Ligand 4 was found to provide both /pi/- and N-bonded complexes. A single-crystal X-ray structural analysis of a derivative of Cp*Rh(quinoline)(acetonitrile)/sub 2//sup 2+/, (Cp*Rh(quinoline)(/mu/-hydroxo))/sub 2//sup 2+/ synthetic precursors were excellent catalysts or catalyst precursors for the selective hydrogenation of 1, 2, and 4 to their corresponding tetrahydro derivatives. This latter result defines the important role of N-bonding for regioselective nitrogen ring reduction.

Research Organization:
Lawrence Berkeley Lab., CA (USA)
DOE Contract Number:
AC03-76SF00098
OSTI ID:
6048282
Journal Information:
Organometallics; (United States), Vol. 7:10
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
QUINOLINES
HYDROGENATION
RHODIUM COMPLEXES
CATALYTIC EFFECTS
CHEMICAL REACTIONS
BINDING ENERGY
CATALYSIS
CATALYSTS
CATIONS
CHEMICAL BONDS
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
LIGANDS
NITROGEN
AROMATICS
AZAARENES
AZINES
CHARGED PARTICLES
COMPLEXES
DATA
ELEMENTS
ENERGY
HETEROCYCLIC COMPOUNDS
INFORMATION
IONS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties