The complexation reaction of oxotitanium(IV) tetraphenylporphyrin with benzoyl peroxide: a DFT study
- 35 Downloads
Quantum chemical calculations based on density functional theory were used to analyze the potentially possible reactions between oxotitanium(IV) tetraphenylporphyrin ((TPP)Ti = O) and benzoyl peroxide (BP). Wavefunction analyses were performed, and electrostatic potential maps were calculated for (TPP)Ti = O and BP molecules. It was shown that the oxygen extra ligand is the most reactive part in (TPP)Ti = O. The structures of the possible inner- and outer-sphere complexes of (TPP)Ti = O with BP and their IR spectra were calculated, and the energies of their formation were estimated. The formation of an outer-sphere complex is the most thermodynamically probable process in the reaction of (TPP)Ti = O and BP. This interaction does not alter the state of the peroxy bond in the initiator molecule. A scheme was suggested to explain the reasons for the accelerating effect of oxotitanium(IV) porphyrins on the radical polymerization of methyl methacrylate reported in the literature. This scheme presumes that the polymerizing system contains a metal-centered radical, a product of the growing radical addition to the metalloporphyrin. This particle can form an inner-sphere complex with BP, which then undergoes homolytic decomposition.
KeywordsOxotitanium(IV) tetraphenylporphyrin Benzoyl peroxide Quantum chemical simulation IR spectra calculations Density functional theory
The calculations were performed using the equipment at the Center for collective use “Khimiya” (Chemistry) at Ufa Institute of chemistry UFRC RAS within the State task for 2017–2019 (AAAA-A17-117011910026-3).
- 1.Kadish KM, Smith KM, Guilard R (eds) (2000) The porphyrin handbook: applications: past, present and future, vol 6. Academic Press, New YorkGoogle Scholar
- 3.Heuts JPA, Forster DJ, Davis TP (2000) Mechanistic aspects of catalytic chain transfer polymerization. In: Boffa LS, Novak BM (eds) Transition metal catalysis in macromolecular design, Chapter 16. ACS Publications, Washington, pp 254–272. https://doi.org/10.1021/bk-2000-0760.ch016 CrossRefGoogle Scholar
- 9.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2013) Gaussian 09, Revision D.01. Gaussian Inc, Wallingford CTGoogle Scholar