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Quantum chemical study of the Si–C bond photodissociation in benzylsilane derivatives: a specific ‘excited-state’ silicon effect by Mikhayl F Budyka; Tatyana S Zyubina; Antonios K Zarkadis is a Chemistry article available to read on EtoBox.

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Structure and properties of the ground ðS 0 Þ and lowest excited triplet ðT 1 Þ states of benzylsilane derivatives bearing the benzophenone chromophore group, p-PhCO-C 6 H 4 -CR 00 R 000 -SiR 0 3 (R 0 , R 00 , R 000 1⁄4 H, H, H; Me, H, H; Me, H, Me; Me, Me, Me; Me, H, Ph; Me, Me, Ph; Me, Ph, Ph), were calculated using the semiempirical PM3 method. The bond dissociation energy (BDE) of the Si-C bond in the S 0 state and the heat of the bond dissociation reaction ðDH r Þ in the T 1 state were found to decrease with increasing substitution at silicon and/or benzylic carbon atom. There exists a straight-line dependence between the BDE and DH r values in the series of the compounds studied. Minimal energy paths for the 'heterobenzylic' Si -C bond dissociation in benzylsilane PhCH 2 -SiH 3 and for the benzylic C-C bond dissociation in the carbon analogue ethylbenzene PhCH 2 -CH 3 in T 1 states were calculated using PM3 and B3LYP/6-31G\*\*. The activation energies obtained are 13.3 and 36.7 kcal/mol (PM3), and 6.3 and 19.6 kcal/mol (B3LYP/6-31G\*\* with ZPE correction) for benzylsilane and ethylbenzene, respectively. Both methods predict much lower activation barrier for benzylsilane comp

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Author

Mikhayl F Budyka; Tatyana S Zyubina; Antonios K Zarkadis

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0166-1280)

Published

2004

Language

EN

Field

Chemistry (Physical Sciences)