ja071698k_si_006.cif (41.53 kB)
Cleavage of Carbon−Carbon Bonds of Diphenylacetylene and Its Derivatives via Photolysis of Pt Complexes: Tuning the C−C Bond Formation Energy toward Selective C−C Bond Activation
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posted on 2007-07-18, 00:00 authored by Ahmet Gunay, William D. JonesCarbon−carbon bond activation of diphenylacetylene and several substituted derivatives has
been achieved via photolysis and studied. Pt0−acetylene complexes with η2-coordination of the alkyne,
along with the corresponding PtII C−C activated photolysis products, have been synthesized and
characterized, including X-ray crystal structural analysis. While the C−C cleavage reaction occurs readily
under photochemical conditions, thermal activation of the C−C bonds or formation of PtII complexes was
not observed. However, the reverse reaction, C−C reductive coupling (PtII → Pt0), did occur under thermal
conditions, allowing the determination of the energy barriers for C−C bond formation from the different PtII
complexes. For the reaction (dtbpe)Pt(−Ph)(−C⋮CPh) (2) → (dtbpe)Pt(η2-PhC⋮CPh) (1), ΔG⧧ was 32.03(3) kcal/mol. In comparison, the energy barrier for the C−C bond formation in an electron-deficient system,
that is, (dtbpe)Pt(C6F5)(C⋮CC6F5) (6) → (dtbpe)Pt(η2-bis(pentafluorophenyl)acetylene) (5), was found to
be 47.30 kcal/mol. The energy barrier for C−C bond formation was able to be tuned by electronically
modifying the substrate with electron-withdrawing or electron-donating groups. Upon cleavage of the C−C
bond in (dtbpe)Pt(η2-(p-fluorophenyl-p-tolylacetylene) (9), both (dtbpe)Pt(p-fluorophenyl)(p-tolylacetylide)
(10) and (dtbpe)Pt(p-tolyl)(p-fluorophenylacetylide) (11) were obtained. Kinetic studies of the reverse reaction
confirmed that 10 was more stable toward the reductive coupling [the term “reductive coupling” is defined
as the formation of (dtbpe)Pt(η2-acetylene) complex from the PtII complex] than 11 by 1.22 kcal/mol, under
the assumption that the transition-state energies are the same for the two pathways. The product ratio for
10 and 11 was 55:45, showing that the electron-deficient C−C bond is only slightly preferentially cleaved.