The physical organic chemistry of Fischer carbene complexes

Department of Chemistry and Biochemistry, University of California, Santa Cruz, California, USA 

What are Fischer carbene complexes 137 Scope of this chapter 142 Reactions at the metal 143 Thermolysis 144 

Substitution of CO by phosphines 145 The Dotz reaction 149 Rearrangement reactions with loss of CO 151 Photochemical reactions 153 Reactions at the carbene carbon 158 General features 158 Amine nucleophiles 159 Phospine and phosphite nucleophiles 167 Alcohols and alkoxide ion nucleophiles 171 Thiol and thiolate ion nucleophiles 179 Intramolecular nucleophilic reactions 191 Hydroxide ion and water as nucleophiles 194 Insertion reactions initiated by nucleophilic attack Acid-base reactions at the a-carbon 207 General features and methods 207 Kinetic and thermodynamic acidities 209 Effect of structure on pKa values 210 Intrinsic rate constants for proton transfer 219 Thermodynamic acidities in organic solvents 223 Hydrolysis of ionizable carbene complexes 228 Acknowledgments 232 References 233 

Fischer carbene complexes belong to a class of compounds commonly referred to as transition metal carbene complexes. The 1983 book by Dotz et al provides an excellent introduction to many of the most important general aspects of these 

ADVANCES IN PHYSICAL ORGANIC CHEMISTRY VOLUME 37 ISSN 0065-3160 

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The physical organic chemistry of Fischer carbene complexes has been reviewed 176,177 only studies relevant to the PNS will be discussed in this chapter. 

Reviews have appeared on the absolute kinetics of intramolecular alkylcarbene reactions,1 the reactions between carbenes and the O—H bond,2 carbenes and carboranes,3 the use of carbenes and carbenoids in the synthesis of heterocycles,4 and the physical organic chemistry of Fischer carbene complexes.5... 

C. F. Bernasconi, Developing the Physical Organic Chemistry of Fischer Carbene Complexes, Chem. Soc. Rev. 26, 299-307 (1997). 

Bemasconi, C. F. Developing the physical organic chemistry of Fischer carbene complexes. Chem. See. Rev. 1997, 26, 299-308. 

The Physical Organic Chemistry of Fischer Carbene Complexes... 

THE PHYSICAL ORGANIC CHEMISTRY OF FISCHER CARBENE COMPLEXES... 

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See also in sourсe #XX -- [ , ]

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