Metal Hydrides and Organometallics

Similar results were reported by Streitwieser et al. [142] for the addition of LiH to formaldehyde, investigated at the 3-21G level. The transition state for the monomer addition is very early, with about 10% reaction progress as measured by the change in the C = O bond length or by pyramidalization at the carbonyl carbon. 

Houk et al. have made calculations for the reactions of lithium enolate and enol borinate of acetaldehyde with formaldehyde at the 3-21G level [125j. In the first case. 

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Kaim, W. Thermal and Light Induced Electron Transfer Reactions of Main Group Metal Hydrides and Organometallics. 169, 231-252 (1994). 

Acid chlorides are easily converted to 1° alcohols and aldehydes (see Section 5.7.21) and 3° alcohols and ketones through the choice of appropriate metal hydride and organometallic reagents (see Section 5.5.5). Acid chloride reacts with benzene in the presence of Lewis acid (AICI3) in Friedel-Crafts acylation (see Section 5.5.6). 

In spite of their practical importance for organic synthesis and industrial catalysis, main group metal hydrides and organometallic compounds without active d orbitals at the metal center have received relatively little attention with regard to their obvious potential for electron transfer reactivity. One reason for this neglect lies in frequent complications arising from solvent-dependent self-association... 

Reactions were studied between naphtho[l,8-Z c]thiete (34, Scheme 10) and nucleophiles including metal hydrides and organometallic compounds (76JA6643). 

Examples of metal hydride and organometallic additions include reactions of lithium hydride and sodium hydride with acetaldehyde and its homologs [145-147], reactions of methyllithium and methylcopper with acrolein [148], and aldol additions of lithium enolates [125]. The geometry of the four-center, cyclic transition states for such additions seems to depend on the size of the metal atom (see Schemes 6.16 and 6.17). 

Reaction with metal hydrides and organometallic compounds... 

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