Reactions of eta/sup 5/-C/sub 5/H/sub 5/(CO)/sub 2/Fe(C(XR)YR)/sup +/ carbene complexes, where X and Y are O, S, Se, and/or NR, with amines

Journal Article · Tue Mar 31 23:00:00 EST 1981 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50218a032· OSTI ID:6206526

McCormick, F B; Angelici, R J

Reactions of Cp(CO)/sub 2/Fe(C(XR)YR)/sup +/ where Cp = eta/sup 5/-C/sub 5/H/sub 5/ with amines occur at the carbene ligand when X, Y = O, S, and/or Se and the product distribution is dependent upon the leaving-group abilities of the carbene substituents (PhSe-approx. = PhS/sup -/, PhO/sup -/ > CH/sub 3/S/sup -/ > CH/sub 3/O). When both carbene substituents are good leaving groups (PhSe/sup -/, PhS/sup -/, PhO/sup -/, or CH/sub 3/S/sup -/), Cp(CO)/sub 2/Fe(C(XR)YR)/sup +/ reacts with primary amines to give isocyanide complexes, Cp(CO)/sub 2/FeCNR/sup +/, and with secondary amines to form carbene derivatives, Cp(CO)/sub 2/Fe(C(XR)NR/sub 2/)/sup +/. When only one carbene substituent is a good leaving group, Cp(CO)/sub 2/Fe(C(XR)YR)/sup +/ yields carbene derivatives, Cp(CO)/sub 2/Fe/sup +/(C(XR)NRR')/sup +/(XR = OCH/sub 3/; R' = R, H), upon reaction with primary or secondary amines. Substituents are poor leaving groups (CH/sub 3/O/sup -/), a complex mixture of products generally results on reaction with amines. A mechanism involving formation of an ylide intermediate, Cp(CO)/sub 2/Fe(C(XR)(YR)NR/sub 3/)/sup +/, is proposed to account for these results. Spectroscopic studies (ir and /sup 13/C NMR) show that N ..-->.. C (carbene) ..pi.. donation increases as the basicity of the amine group increases for the Cp(CO)/sub 2/Fe(C(OCH/sub 3/)NR/sub 2/)/sup +/ complexes.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6206526
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 20:4; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AMINES
CARBENES
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
INFORMATION
INFRARED SPECTRA
IRON COMPLEXES
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RADICALS
RESONANCE
SELENIUM COMPOUNDS
SPECTRA
TRANSITION ELEMENT COMPLEXES