Related Experiment Video
Updated: May 31, 2026
Preparation of 6-aminocyclohepta-2,4-dien-1-one Derivatives via Tricarbonyl(tropone)iron
Published on: August 12, 2019
Highly unsaturated binuclear butadiene iron carbonyls: quintet spin states, perpendicular structures, agostic
Yi Zeng1, Shijian Wang, Hao Feng
1School of Physics and Chemistry, Research Center for Advanced Computation, Xihua University, Chengdu, China; E-Mails: zengyi08@hotmail.com (Y.Z.); xhuwsj@163.com (S.W.).
Abstract:
The highly unsaturated binuclear butadiene iron carbonyls (C(4)H(6))(2)Fe(2)(CO)(n) (n = 2, 1) have been examined using density functional theory. For (C(4)H(6))(2)Fe(2)(CO)(n) (n = 2, 1), both coaxial and perpendicular structures are found. The global minima of (C(4)H(6))(2)Fe(2)(CO)(n) (n = 2, 1) are the perpendicular structures 2Q-1 and 1Q-1, respectively, with 17- and 15-electron configurations for the iron atoms leading to quintet spin states. The Fe=Fe distance of 2.361 Å (M06-L) in the (C(4)H(6))(2)Fe(2)(CO)(2) structure 2Q-1 suggests a formal double bond. The Fe≡Fe bond distance in the (C(4)H(6))(2)Fe(2)(CO) structure 1Q-1 is even shorter at 2.273 Å (M06-L), suggesting a triple bond. Higher energy (C(4)H(6))(2)Fe(2)(CO)(n) (n = 2, 1) structures include structures in which a bridging butadiene ligand is bonded to one of the iron atoms as a tetrahapto ligand and to the other iron atom through two agostic hydrogen atoms from the end CH(2) groups. Singlet (C(4)H(6))(2)Fe(2)(CO) structures with formal Fe-Fe quadruple bonds of lengths ∼2.05 Å were also found but at very high energies (∼47 kcal/mol) relative to the global minimum.
Related Concept Videos
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
02:42Valence Bond Theory
02:45Valence Bond Theory
01:24π Molecular Orbitals of 1,3-Butadiene
The simplest conjugated diene is 1,3-butadiene: a four-carbon system where each carbon is sp2-hybridized and has an unhybridized p orbital that contains an unpaired electron. According to molecular orbital theory, atomic orbitals combine to form molecular orbitals such that the number...
02:34Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
01:22Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...