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 · Wed Apr 01 00:00:00 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), Vol. 20:4
• Country of Publication: United States
• Language: English

Related Subjects

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