Selectivity in the activation of fluorinated aromatic hydrocarbons by [(C[sub 5]H[sub 5])Rh(PMe[sub 3])] and [(C[sub 5]Me[sub 5])Rh(PMe[sub 3])]

Journal Article · Tue Feb 01 04:00:00 EST 1994 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00014a025· OSTI ID:7302114

Selmeczy, A D; Jones, W D ^[1]; Partridge, M G; Perutz, R N ^[2]

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1. Univ. of Rochester, NY (United States)
2. Univ. of York, Heslington (United Kingdom)

Thermolysis of (C[sub 5]Me[sub 5])Rh(PMe[sub 3])(Ph)H (1) in neat fluorobenzene, o-difluorobenzene, p-difluorobenzene, or 1,3,5-trifluorobenzene results in the formation of the new aryl hydride complexes (C[sub 5]Me[sub 5])Rh(PMe[sub 3])(aryl[sub F])H (aryl[sub F] = 2-C[sub 6]H[sub 4]F, 2,3-C[sub 6]H[sub 3]F[sub 2], 2,5-C[sub 6]H[sub 3]F[sub 2], or 2,4,6-C[sub 6]H[sub 2]F[sub 3]). Short term thermolysis of 1 in m-difluorobenzene produces a kinetic mixture of products resulting from activation of all possible C-H bond positions. Continued thermolysis of this mixture results in exclusive formation of the thermodynamic product (C[sub 5]Me[sub 5])Rh(PMe[sub 3])(2,6-C[sub 6]H[sub 3]F[sub 2])H. Irradiation of (C[sub 5]Me[sub 5])Rh(PMe[sub 3])H[sub 2] in o-difluorobenzene at -30[degree]C gives both (C[sub 5]Me[sub 5])Rh(PMe[sub 3])(2,3-C[sub 6]H[sub 3]F[sub 2])H and (C[sub 5]Me[sub 5])Rh(PMe[sub 3])(3,4-C[sub 6]H[sub 3]F[sub 2])H as the kinetic products. Thermolysis of this mixture results in exclusive formation of the thermodynamic product (C[sub 5]Me[sub 5])Rh(PMe[sub 3])(2,3-C[sub 6]H[sub 3]F[sub 2])H. These aryl hydrides are readily converted to their bromo derivatives by reaction with bromoform. Photochemical reaction of (C[sub 5]H[sub 5])Rh(PMe[sub 3])(C[sub 2]H[sub 4]) (2) with o-, m-, and p-difluorobenzene, 1,3,5-trifluorobenzene, 1,2,4,5-tetrafluorobenzene, or pentafluorobenzene at room temperature gives single aryl hydride products (C[sub 5]H[sub 5])Rh(PMe[sub 3])(aryl[sub F])H (aryl[sub F] = 2,3-C[sub 6]H[sub 3]F[sub 2], 2,6-C[sub 6]H[sub 3]F[sub 2], 2,5-C[sub 6]H[sub 3]F[sub 2], 2,4,6-C[sub 6]H[sub 2]F[sub 3], 2,3,5,6-C[sub 6]HF[sub 4], or C[sub 6]F[sub 5]) in which C-H insertion occurs adjacent to a fluorine. These compounds are also converted to their bromo derivatives by reaction with bromoform. The (C[sub 5]Me[sub 5])Rh(PMe[sub 3])(aryl[sub F])Br complexes were structurally characterized. 19 refs., 5 figs., 6 tabs.

• DOE Contract Number: FG02-86ER13569
• OSTI ID: 7302114
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 13:2; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
AROMATICS
BROMINATED ALIPHATIC HYDROCARBONS
BROMOFORM
CHEMICAL ACTIVATION
CHEMICAL BONDS
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPILED DATA
COMPLEXES
CRYSTALLIZATION
DATA
DIFFRACTION
FLUORINATED AROMATIC HYDROCARBONS
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENATED AROMATIC HYDROCARBONS
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHASE TRANSFORMATIONS
PHOTOCHEMICAL REACTIONS
RESONANCE
RHODIUM COMPLEXES
SCATTERING
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION