Preparation and characterization of organoiron secondary alkoxycarbene complexes

Journal Article · Sun Dec 31 23:00:00 EST 1978 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00497a020· OSTI ID:6282027

Cutler, A R

A series of organoiron secondary alkoxycarbene salts, CpFe(CO)L (C(OR)H)/sup +/ PF/sub 6//sup -/ (L = CO, Ph/sub 3/P; R = Me, Et) (a-d) has been synthesized by hydride abstraction from the requisite alkoxymethyl complexes (a-d) with a trityl salt. The dealkylation of 2 with iodide was investigated as a synthetic approach to eta/sup 1/-formyl complexes, CpFe(CO)L(CHO) (3). One equivalent of iodide dealkylated 2a-c to mixtures of CpFe(CO)/sub 2/L/sup +/ (6a,b), 1a-c, and alkyl iodide, by a reaction sequence involving hydride transfer from a transient 3 to 2. The hydride acceptor properties of 2 were also investigated by their reactions with borohydride. The observed reduction of coordinated alkoxycarbenes to alkoxymethyl and methyl ligands is of possible relevance to the catalytic fixation of carbon monoxide (e.g., Fischer--Tropsch processes) to hydrocarbons, since surface-bound secondary hydroxycarbene ligands have been postulated in forming the initial C--H bonds.

• Research Organization: Wesleyan Univ., Middletown, CT
• OSTI ID: 6282027
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:3; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKOXY RADICALS
BOROHYDRIDES
BORON COMPOUNDS
CARBENES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
FISCHER-TROPSCH SYNTHESIS
HALIDES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
IODIDES
IODINE COMPOUNDS
IRON COMPLEXES
KINETICS
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
RADICALS
REACTION KINETICS
REACTIVITY
SYNTHESIS
TRANSITION ELEMENT COMPLEXES