Structure determination of triplet diphenylcarbenes by in situ X-ray crystallographic analysis.
Crystalline-state photoreactions of the following diphenyldiazomethanes were investigated by in situ X-ray crystallography, spectroscopy, and theoretical calculations: bis(2,4,6-trichlorophenyl)diazomethane (1-N2), bis(2,4,6-tribromophenyl)diazomethane (2-N2), bis(2,6-dibromo-4-methylphenyl)diazomethane (3-N2), bis(2,6-dibromo-4-tert-butylphenyl)diazomethane (4-N2), (2,4,6-tribromophenyl)-(2,6-dimethyl-4-tert-butylphenyl)diazomethane (5-N2), bis(4-bromophenyl)diazomethane(6-N2), and diazofluorene (7-N2). Crystal structures of photoinduced triplet diphenylcarbenes (DPCs) of 1, 2, and 4 were determined. We found remarkable differences between their structural information obtained in the crystalline state and that previously obtained spectroscopically in a glass matrix. Although the triplet DPCs of 1, 2, and 4 have significantly different stabilities in solution, only subtle differences in their structural parameters, except for their C(:)-Ar bond lengths, are observed. It is noteworthy that the average bond length of C(:)-Ar for 4 (1.374 A) is considerably shorter than those for (3)1 and (3)2 (1.430 and 1.428 A, respectively), provided that the two C(:)-Ar bonds being compared were chemically equivalent. The most likely explanations for the small and large differences in bond lengths in 1, 2, and 4 may be derived from the packing effect. The packing patterns of 1 and 2 are identical, but that of 4 is totally different from those of 1 and 2. Moreover, these results are interpreted as indicating that triplet DPCs undergo relaxation upon softening of the environments. Theoretical calculations indicate that the potential energy surface of triplet DPCs in terms of the carbene angle is extremely flat and changes in the angles have little effect on the energies. Triplet DPCs with a sterically congested carbene center are trapped in a structure dictated by the precursor structure in a rigid matrix, even if this is not the thermodynamically most stable geometry, but undergo geometrical relaxation upon softening the matrix to relieve steric compression. ESR studies indicate that the interplanar angles are more flexible than the bond angles.
Kawano
Masaki
M
Department of Chemistry and Materials Science, Tokyo Institute of Technology, Tokyo 152-8551, Japan. mkawano@appchem.t.u-tokyo.ac.jp
Hirai
Katsuyuki
K
Tomioka
Hideo
H
Ohashi
Yuji
Y
D001391:Azo Compounds / Q000737:chemistry*; D001555:Benzene Derivatives / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism
D001391:Azo Compounds; D001555:Benzene Derivatives