Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 7, Pages 2499-2507Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja808683z
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Funding
- Department of Energy
- NSF [CHE-9208463, CHE-9709065]
- NIH [1 S10 RR0 8389-01]
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Cyclopentadienone iron alcohol complexes generated from the reactions of [2,5-(SiMe(3))(2)-3,4-(CH(2))(4)(eta(5)-C(4)COH)]Fe(CO)(2)H (3) and aldehydes were characterized by (1)H NMR, (13)C NMR, and IR spectroscopy. The benzyl alcohol complex [2,5-(SiMe(3))(2)-3,4-(CH(2))(4) (eta(4)-C(4)C=O)]Fe(CO)(2)(HOCH(2)C(6)H(5)) (6-H) was also characterized by X-ray crystallography. These alcohol complexes are thermally unstable and prone to dissociate the coordinated alcohols. The alcohol ligand is easily replaced by other ligands such as PhCN, pyridine, and PPh(3). Dissociation of the alcohol ligand in the presence of H(2) leads to the formation of iron hydricle 3. The reduction of aldehydes by 3 was carried out in the presence of both potential intermolecular and intramolecular traps. The reaction of 3 with PhCHO in the presence of 4-methylbenzyl alcohol as a potential intermolecular trapping agent initially produced only iron complex 6-H of the newly formed benzyl alcohol. However, the reaction of 3 with 4-(HOCD(2))C(6)H(4)CHO, which possesses a potential intramolecular alcohol trapping agent, afforded two alcohol complexes, one with the newly formed alcohol coordinated to iron and the other with the trapping alcohol coordinated. The intramolecular trapping experiments support a mechanism involving concerted transfer of a proton from OH and hydricle from Fe of 3 to aldehydes. The kinetics and mechanism of the hydrogenation of benzaldehyde catalyzed by 3 are presented.
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