TY - JOUR
T1 - Migratory-insertion of carbon monoxide into metal-acyl bonds
AU - Geoffroy, Gregory
AU - Sheridan, John
AU - Bassner, Sherri
AU - Kelley, Colleen
N1 - Funding Information:
We gratefully acknowledge the U.S. Department of Energy, Office of Basic Energy Sciences for supporting the work described herein.
PY - 1989/1/1
Y1 - 1989/1/1
N2 - The a-ketoacyl complex Cp’(CO)(NO)Mn-C{0}C{0}Tol, 4 (Cp’=C5H4Me), has been prepared by two independent routes involving the oxidation of the carbyne ligand in [Cp'(CO)2Mn≡CTol]+ with nitrite ion and oxidation of the anionic acyl complex [Cp(CO)2Mn-C{0}Tol]- followed by addition of NO gas. A common intermediate in both reactions is the. 17e- acyl complex [Cp(CO)2Mn-C(0)Tol]. which undergoes migratory-insertion of CO into the metal-acyl bond upon addition of NO. Aspects of the reactivity of complex 4 and its PPh3 substituted derivative 9 with electrophiles, nucleophiles, alkynes, and oxidizing agents are discussed. A surprisingly facile carbon-carbon bond cleavage of the a-ketoacyl ligand of complex 9 occurs upon either oxidation or protonation of the complex, and the a-ketoacyl ligand of complex 4 readily couples with alkynes to form metallacycles. Demetallation of the latter by treatment with acid releases vinyl-a-dione products.
AB - The a-ketoacyl complex Cp’(CO)(NO)Mn-C{0}C{0}Tol, 4 (Cp’=C5H4Me), has been prepared by two independent routes involving the oxidation of the carbyne ligand in [Cp'(CO)2Mn≡CTol]+ with nitrite ion and oxidation of the anionic acyl complex [Cp(CO)2Mn-C{0}Tol]- followed by addition of NO gas. A common intermediate in both reactions is the. 17e- acyl complex [Cp(CO)2Mn-C(0)Tol]. which undergoes migratory-insertion of CO into the metal-acyl bond upon addition of NO. Aspects of the reactivity of complex 4 and its PPh3 substituted derivative 9 with electrophiles, nucleophiles, alkynes, and oxidizing agents are discussed. A surprisingly facile carbon-carbon bond cleavage of the a-ketoacyl ligand of complex 9 occurs upon either oxidation or protonation of the complex, and the a-ketoacyl ligand of complex 4 readily couples with alkynes to form metallacycles. Demetallation of the latter by treatment with acid releases vinyl-a-dione products.
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U2 - 10.1351/pac198961101723
DO - 10.1351/pac198961101723
M3 - Article
AN - SCOPUS:0011504226
SN - 0033-4545
VL - 61
SP - 1723
EP - 1729
JO - Pure and Applied Chemistry
JF - Pure and Applied Chemistry
IS - 10
ER -