Selective transformation of carbonyl ligands to organic molecules: Progress report, 1 September 1986--31 August 1989
Studies on anionic phosphido alkyl and acetyl complexes Cp(CO)(PPh/sub 2/)Fe /minus/ R/sup /minus// (1) and In(CO)(PPh/sub 2/)Fe /minus/ R/sup /minus// (2) (R = CH/sub 3/ (a), COCH/sub 3/ (b); In = /eta//sup 5/-indenyl) and their neutral phosphine derivatives Cp(CO)(PPh/sub 2/H)Fe /minus/ R (3) and In(CO)(PPh/sub 2/H)Fe /minus/ R (4) are complete. Attempts to carbonylate 1a and 2a to 1b and 2b failed; also, 3a and 4a resist carbonylation. Reacting 1b with MeI affords a neutral PPh/sub 2/Me acetyl compound 5, whereas MeOSO/sub 2/CF/sub 3/ gives the Fischer carbene complex Cp(PPh/sub 2/)(CO) Fe = C(OMe)CH/sub 3/ (6). Carbene 6 isomerizes to 5 at room temperature. Reaction conditions have been optimized for tenerating vinylidene compounds In/sub 2/(CO)/sub 3/Fe/sub 2/ ..mu..-(C = CHR) from InFe(CO)/sub 2//sup /minus// and In(CO)/sub 2/Fe /minus/ CH/sub 2/R (R = H, Me, OMe). The bimetallic carbonylation procedure for converting Fp/sup /minus//(Li/sup +/, Na/sup +/, PPN/sup +/) and In(CO)/sub 2/Fe /minus/ CH/sub 3/ to InCp(CO)/sub 3/Fe/sub 2/(COCH/sub 3//sup /minus//) and then regioselectively to FpCOCH/sub 3/ (1 atm CO) has been optimized. Studies are finished on the diastereofacial selectivity observed during reduction of the alkoxycarbenes Cp(P(OR)/sub 3/)(CO)Fe = C(OCH/sub 3/)CH/sub 3//sup +/ (R = Me, Ph) with borohydride reagents R/sub 3/BH/sup /minus// (Li/sup +/, Na/sup +/, K/sup +/) and with (PPh/sub 3/CuH)/sub 6/. A survey of the Rh(I)-catalyzed hydrosilation of a variety of iron acyl complexes has been concluded.
- Research Organization:
- Rensselaer Polytechnic Inst., Troy, NY (United States)
- DOE Contract Number:
- FG02-86ER13617
- OSTI ID:
- 6290884
- Report Number(s):
- DOE/ER/13617-3; ON: DE89011226
- Resource Relation:
- Other Information: Portions of this document are illegible in microfiche products
- Country of Publication:
- United States
- Language:
- English
Similar Records
Highly nucleophilic acetylide, vinyl, and vinylidene complexes. Final progress report, 1 January 1991--31 March 1994
Selective transformation of carbonyl ligands to organic molecules
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
CHEMICAL REACTIONS
COBALT COMPLEXES
INDIUM COMPOUNDS
IRON COMPLEXES
PHOSPHORUS COMPOUNDS
RUTHENIUM COMPLEXES
CARBENES
CARBONYLATION
CHEMICAL REACTION KINETICS
COMPLEXES
LIGANDS
MOLECULAR STRUCTURE
MOLECULES
ORGANIC COMPOUNDS
PROGRESS REPORT
DOCUMENT TYPES
KINETICS
RADICALS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties