Bergman cyclization, metalloenediyne

Benites PJ, Holmberg RC, Rawat DS, et al. Metal-ligand charge-transfer-promoted photoelectronic Bergman cyclization of copper metalloenediynes photochemical DNA cleavage via C-4 H-atom absorption. J Am Chem Soc 2003 125 6434-46. 

Kraft, B. J., Coalter, N. L., Nath, M., Clark, A. E., Siedle, A. R., Huffman, J. C., Zaleski, J. M. Photothermally Induced Bergman Cyclization of Metalloenediynes via Near-Infrared Ligand-to-Metal Charge-Transfer Excitation. Inorg. Chem. 2003,42, 1663-1672. 

V. METALLOENEDIYNE FRAMEWORKS METAL-MEDIATED BERGMAN CYCLIZATION... 

Much like the sparse demonstrations of electronically activated metalloenediyne Bergman cyclization, only two examples of photochemically induced... 

Figure 35. Frontier MOs (obtained from TDDFT involved in the photoelectronic Bergman cyclization of copper metalloenediynes. The metal frontier orbitals (yellow) are highlighted along with the pyridine it and it sets for a respective copper oxidation states.

SCHEME 30.13 Top photo-Bergman cyclization of copper metalloenediynes via metal-ligand charge transfer complex. Bottom relative energies of copper and ligand MOs proposed to be involved in the photoelectronic Bergman cyclization of Cu(I) and Cu(II)-metalloenediynes. Adapted with permission from Benites et al. [27b]. American Chemical Society. 

Benites, P.J., Rawat, D.S. and Zaleski, J.M. (2000) Metalloenediynes ligand field control of thermal Bergman cyclization reactions. Journal of the American Chemical Society, 122(30), 7208-7217. 

Schmitt EW, Huffmaim JC et al (2001) Thermal reactivities of isostructural d ° metalloenediynes metal-dependent Bergman cyclization. Chem Common 167-168... 

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