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), Journal Name: Organometallics; (United States) Vol. 12:9; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBOXYLIC ACIDS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NMR SPECTRA
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PORPHYRINS
RESONANCE
RHODIUM COMPLEXES
SPECTRA
TRANSITION ELEMENT COMPLEXES