Reactions of isocyanides with rhodium porphyrins. Formation of formimidoyl and carbamoyl complexes and CN-R bond cleavage
- Univ. of Pennsylvania, Philadelphia, PA (United States)
Reactions of alkyl and aryl isocyanides with (octaethylporphyrinato)rhodium hydride, (OEP)Rh-H, (octaethylporphyrinato)rhodium(II) dimer, [(OEP)Rh][sub 2] and (tetramesitylporphyrinato)rhodium(II), (TMP)Rh, have been investigated for comparison with CO reactivity. Alkyl and aryl isocyanides interact with (OEP)Rh-H to form 1:1 adducts, (OEP)Rh(H)(CNR), which react further to produce formimidoyl complexes, (OEP)Rh-CH=NR, in analog with the reaction of (OEP)Rh-H with CO that produces a formyl complex, (OEP)Rh-CHO. [(OEP)Rh][sub 2] forms 1:1 complexes with isocyanides where the 2,6-dimethylphenyl isocyanide derivative persists at equilibrium, but alkyl isocyanides undergo CN- alkyl bond cleavage to form alkyl, (OEP)Rh-R and cyanide, (OEP)Rh(CN)(CNR), complexes. No evidence was obtained for bridging isocyanide species analogous to the dimetal ketone RhC(O)Rh and dimetal diketone RhC(O)C(O)Rh complexes observed in reactions of [(OEP)Rh][sub 2] with CO. Carbamoyl complexes, (OEP)Rh-C(O)NHR, are formed in reactions of [(OEP)Rh][sub 2] with CNR and H[sub 2]O or CO and RNH[sub 2]. 24 refs., 7 figs., 3 tabs.
- DOE Contract Number:
- FG02-86ER13615
- OSTI ID:
- 5651916
- Journal Information:
- Organometallics; (United States), Vol. 12:9; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBON MONOXIDE
CHEMICAL REACTIONS
PORPHYRINS
RHODIUM COMPLEXES
CRYSTAL STRUCTURE
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
NMR SPECTRA
ORGANOMETALLIC COMPOUNDS
CARBON COMPOUNDS
CARBON OXIDES
CARBOXYLIC ACIDS
CHALCOGENIDES
COMPLEXES
DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RESONANCE
SPECTRA
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures