Kunio Mochida

Polystyrene-supported hydrogermanes (1-4) were prepared by functionalization of polystyrenes or functionalization of a styrene followed by polymerization. The hydrogermanes, 1-4, reduced organic halides with or without a catalyst to give alkanes under mild conditions in the order: C-I>C-Br>C-Cl. The hydrogermanes, 1-4, were easily separated after use by filtering and could be regenerated with lithium aluminum hydride after their reactions with organic halides. (C) 2003 Elsevier Ltd. All rights reserved.

Thermal reactions of 1,2-dimetallacyclohexa-3,5-dienes (1-3) with tetracyanoethylene (TCNE) were investigated. The reaction of 1,2-disilacyclohexa-3,5-diene (1) with TCNE mainly gave 4-amino-5,6-dicyano-2,2,11,11-tetramethyl-1,8,9,10-tetraphenyl-3-aza-2, 11-disilatricyclo[6.2.1.03,7]undeca-4,6,9-triene through a charge-transfer complex. The reaction of 1,2-digermacyclohexa-3,5-diene (2) with TCNE afforded 4-amino-5,6-dicyano-2,2,11,11-tetramethyl-1,8,9, 10-tetraphenyl-3-aza-2,11-digermatricyclo[6.2.1.03,7] undeca-4,6,9-triene. 2,2,3,3-Tetracyano-7,7-dimethyl-1,4,5,6- tetraphenyl-7-germabicyclo[2.2.1]hept-5-ene was also detected. On the other hand, 1-germa-2-silacyclohexa-3,5-diene (3) reacted with TCNE to give 4-amino-5,6-dicyano-2,2,11,11-tetramethyl-1,8,9,10- tetraphenyl-3- aza-11-germa-2-silatricyclo[6.2.1.03,7] undeca-4,6,9-triene, 4-amino-5,6-dicyano-2,2,11,11-tetramethyl-1,8,9,10- tetraphenyl-3-aza-11- germa-2-silatricyclo[6.3.01,8 .03,7]undeca-4,6,9- triene, and 2,2,3,3-tetracyano-7,7-dimethyl-1,4,5, 6-tetraphenyl-7- germabicyclo[2.2.1]hept-5-ene as main products. The mechanism of the formation of new heterocyclic compounds through electron-transfer reactions of 1,2-dimetallacyclohexa-3,5-dienes with TCNE is discussed. © 2003 Elsevier Science B.V. All rights reserved.

Thermal reactions of 1,2-dimetallacyclohexa-3,5-dienes (1-3) with tetracyanoethylene (TCNE) were investigated. The reaction of 1,2-disilacyclohexa-3,5-diene (1) with TCNE mainly gave 4-amino-5,6-dicyano-2,2,11,11-tetramethyl-1,8,9,10-tetraphenyl-3-aza2,11-disilatricyclo[6.2. 1.0(3,7)]undeca-4,6,9-triene through a charge-transfer complex. The reaction of 1,2-digermacyclohexa-3,5-diene (2) with TCNE afforded 4-amino-5,6-dicyano-2,2,11,11-tetramethyl-1,8,9,10-tetraphenyl-3-aza-2,11-digermatricyclo[6.2. 1.0(3,7)]undeca-4,6,9-triene. 2,2,3,3-Tetracyano-7,7-dimethyl-1,4,5,6-tetraphenyl-7-germabicyclo[2.2.1]hept-5-ene was also detected. On the other hand, 1-germa-2-silacyclohexa-3,5-diene (3) reacted with TCNE to give 4-amino-5,6-dicyano-2,2,1 1,11-tetramethyl-1,8,9,10-tetraphenyl-3-aza-11-germa-2-silatricyclo[6.2. 1.0(3,7)]undeca-4,6,9-triene, 4-amino-5,6-dicyano-2,2,1 1,11-tetramethyl-1,8,9,10-tetraphenyl-3-aza-11-germa-2-silatricyclo[6.3.0(1,8).0(3,7)]undeca-4,6,9-triene, and 2,2,3,3-tetracyano-7,7-dimethyl-1,4,5,6-tetraphenyl-7-germabicyclo[2.2.1]hept-5-ene as main products. The mechanism of the formation of new heterocyclic compounds through electron-transfer reactions of 1,2-dimetallacyclohexa-3,5-dienes with TCNE is discussed. (C) 2003 Elsevier Science B.V. All rights reserved.