Destabilizing d/pi/-p/pi/ orbital interactions and the alkylation reactions of iron(II) - Thiolate complexes

Journal Article · Wed Jan 13 04:00:00 EST 1988 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00274a039· OSTI ID:5833846

Ashby, M T; Enemark, J H; Lichtenberger, D L

For CpFe(CO)/sub 2/SR (1) (R = C/sub 6/H/sub 4/-p-Z; Z = OMe, H, Cl, CF/sub 3/, NO/sub 2/) the /pi/-type interaction between formally occupied metal d orbitals and the sulfur lone pair that is principally 3p in character has been modeled with Fenske-Hall molecular orbital calculations and experimentally investigated by gas-phase photoelectron spectroscopy. A calculation for 1(R = H) predicts that the highest occupied molecular orbital (HOMO) is metal-sulfur antibonding and largely sulfur in character. The observed HOMO ionization energies of 1 correlate with several chemical properties, including the rate of reaction of the thiolate ligand with alkyl halides. Solvent and substituent effects on the reaction rate favor a mechanism involving nucleophilic displacement of the halide by the coordinated thiolate ligand. The nucleophilicity of the coordinated thiolate ligand of 1 is related to the metal-sulfur d/pi/-p/pi/ antibonding interactions. 30 refs., 7 figs., 4 tabs.

• Research Organization: Univ. of Arizona, Tucson (USA)
• DOE Contract Number: AC02-80ER10746
• OSTI ID: 5833846
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:1; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBONYLS
CHLORINE COMPOUNDS
COMPLEXES
DATA
EXPERIMENTAL DATA
FLUORINE COMPOUNDS
HALOGEN COMPOUNDS
INFORMATION
IRON COMPLEXES
NITROGEN COMPOUNDS
NUMERICAL DATA
ORBIT STABILITY
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
STABILITY
TRANSITION ELEMENT COMPLEXES