(Hydroxyacetyl)iridium and -rhodium complexes: model compounds for CO hydrogenation

Journal Article · Wed Mar 19 04:00:00 EST 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00266a056· OSTI ID:5584238

Milstein, D; Fultz, W C; Calabrese, J C

Hydroxyacetyl complexes are postulated as intermediates in the direct conversion of synthesis gas to oxygenated products and in the hydroformylation of formaldehyde to glycolaldehyde, an ethylene glycol precursor. Whereas various hydroxymethyl complexes are now known, Fe(COCH/sub 2/OH)(P(OMe)/sub 3/)/sub 2/(CO)Cl obtained as an isomeric mixture is the only hydroxyacetyl complex reported and no (hydroxyacetyl)metal hydrides are known. A chelate-stabilized hydroxyacyl complex has been reported very recently. The lack of hydroxyacetyl complexes is perhaps due in part to difficulties in carbonylation of hydroxymethyl complexes. Here the synthesis of such complexes by oxidative addition reactions of 2,5-dihydroxy-1,4-dioxane (glycol aldehyde dimer) to Ir(I) and Rh(I) complexes is reported. This is the reversal of the postulated product-forming step in formaldehyde hydroformylation. 20 references, 2 figures.

• Research Organization: E. I. du Pont de Nemours and Co., Wilmington, DE
• OSTI ID: 5584238
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:6; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

090121* -- Hydrocarbon Fuels-- Chemical Synthesis-- (1976-1989)
10 SYNTHETIC FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
INFORMATION
IRIDIUM COMPLEXES
METHANATION
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION INTERMEDIATES
RHODIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES