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Alkene Complexes
General Information
Alkene or olefin ligands are common in organotransition metal chemistry. In fact, the first organotransition metal complex, Zeise's salt (K[PtCl3(C2H4]H2O) was an alkene complex although its true nature was not unambiguously determined until about 100 years after its discovery.
The greater the electron density back-donated into the pi* orbital on the alkene, the greater the reduction in the C=C bond order. An alternative way of stating this would be to say that the hybridization of the alkene carbon changes from sp2 to sp3 as backdonation increases. Either formalism describes two limiting structures: a planar olefin adduct and a metallocyclopropane. X-ray crystallographic studies confirm that the as the C-C bond length increases, the CH2 plane is distorted from the ideal planar geometry of an alkene:
The structural distortion of a bound alkene can also be detected by NMR: the JCH of alkene-like sp2 carbons is typically around 160 Hz whereas sp3-like carbons have a JCH around 120 Hz. Unlike carbonyl stretching frequencies, the C=C IR band (around 1500 cm-1) is usually weak and not well-correlated to C-C bond length. Electronic factors play a large role in the binding of alkenes to transition metals. For example, tetrafluoroethylene will bind more tightly than ethylene to a low valent metal complex because the presence of electron-withdrawing groups on the olefin results in poorer sigma donation and lowers the energy of the pi* orbital (providing better overlap for backbonding). Likewise, ethylene (like carbon monoxide) is a poor ligand for d0 metal complexes because there are no d-electrons to engage in backbonding. The stability of alkene complexes also depends on steric factors as well. An empirical ordering of relative stability would be: tetrasubstituted < trisubstituted < trans-disubstituted < cis-disubstituted < monosubstituted < ethylene.
2. Reduction of a higher valent metal in the presence of an alkene. 3. From alkyls and related species:
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reductive elimination (of an allyl and hydride, for example). hydride abstraction from alkyls protonation of sigma-allyls from epoxides (indirectly)