Abstract
The mechanism of the cycloaddition reaction between singlet H2Ge = Ge: and acetone has been investigated with CCSD(T)//MP2/6-31G* method. From the potential energy profile, it could be predicted that the reaction has two competitive dominant reaction pathways. The reaction rule presented is that the two reactants firstly form a four-membered Ge-heterocyclic ring germylene through the [2 + 2] cycloaddition reaction. Because of the 4p-unoccupied orbital of Ge atom in the four-membered Ge-heterocyclic ring germylene and the π-orbital of acetone forming a π → p donor–acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with acetone to form an intermediate. Because the Ge atom in intermediate happens sp3 hybridization after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. Simultaneously, the ring strain of the four-membered Ge-heterocyclic ring germylene makes it isomerize to a twisted four-membered ring product.
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Stang P (1982) Acc Chem Res 15:348
Stang P (1978) Chem Rev 78:384
Krishnan R, Frisch MJ, Pople JA (1981) Chem Phys Lett 79:408
Frisch MJ, Krishnan R, Pople JA (1981) Chem Phys Lett 81:421
Wardrop DJ, Zhang W (2002) Tetrahedron Lett 43:5389
Feldman KS, Perkins AL (2001) Tetrahedron Lett 42:6031
Apeloig Y, Karni M, Stang PJ, Fox DP (1983) J Am Chem Soc 105:4781
Fox DP, Stang PJ, Apeloig Y, Karni M (1986) J Am Chem Soc 108:750
Lu XH, Wang YX (2003) J Phys Chem 107:7885
Lu XH, Wang YX (2004) J Mol Struct Theochem 686:207
Lu XH, Wu WR, Yu HB, Yang XL, Xu YH (2005) J Mol Struct Theochem 755:39
Lu XH, Yu HB, Wu WR, Xu YH (2007) Int J Quantum Chem 107:451
Lu XH, Xiang PP, Wu WR, Che X (2008) J Mol Struct Theochem 853:82
Hao Q, Lu TX, Jeremiah JW, Andrew CS, Yukio Y, Fang DC, Henry FS (2012) J Phys Chem A 116:4578
Curtis LA, Raghavachari K, Pople JA (1993) J Chem Phys 98:1293
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA, Jr., Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick D. K, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, and Pople JA (2004) Gaussian 03, Revision C.02. Gaussian Inc., Wallingford, CT
Fukui K (1970) J Phys Chem 74:4161
Ishida K, Morokuma K, Komornicki A (1977) J Chem Phys 66:2153
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Ming, J., Li, Y. & Lu, X. Ab initio study of mechanism of cycloaddition reaction between H2Ge = Ge: and acetone. Struct Chem 25, 1669–1675 (2014). https://doi.org/10.1007/s11224-014-0437-z
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DOI: https://doi.org/10.1007/s11224-014-0437-z