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Carbon-carbon bond activation reactions of asymmetric acetylene derivatives of the type L2Pt-(PhCÈýCR) were studied with 1,2-bis(diisopropylphosphino)ethane (dippe), 1,2-bis(di-tert-butyl-phosphino)ethane (dtbpe), and 1-iisopropylphosphino-2-dimethylaminoethane (dippdmae) chelates. (dippe)Pt(¦Ç2-PhCÈýCCH3)(1a), (dippe)Pt(¦Ç2-PhCÈýCCF3)(1b), and (dippe)Pt(¦Ç2-PhCÈýCC-(CH3)3)(1c) showed no thermal reactivity at 160 C, but 1b showed evidence for C-C cleavage to form (dippe)Pt(Ph)(CÈýCCF3) upon irradiation with UV light (>300 nm). In comparison, dtbpe analogues of thesemetal complexes, (dtbpe)Pt(¦Ç2-PhCÈýCCH3)(2a), (dtbpe)Pt(¦Ç2-PhCÈýCCF3)(2b),and (dtbpe)Pt(¦Ç2-PhCÈýCC(CH3)3)(2c), showed either C-HorC-C activation products upon photolysis. 2b produced (dtbpe)Pt(Ph)(CÈýCCF3), but 2a or 2c showed the formation of (dtbpe)Pt(D)(C6D5)(2D) by activation of the C6D6 solvent. Compounds 2a-c showed no thermal reactivity at 160 C. Two complexes with the hemilabile chelate dippdmae were synthesized and fully characterized, (dippdmae)Pt(¦Ç2-PhCÈýCCF3)(3b) and (dippdmae)Pt(¦Ç2-PhCÈýCC(CH3)3)(3c).C-C cleavage products of the type (L2)Pt(Ph)(CÈýCCF3) were observed only upon photolysis of compounds 1b, 2b, and 3b.²»ÖªÄÄλ¸ßÊÖÄܰÑÕâ¶ÎÓ÷½³Ìʽ±íʾ³öÀ´¡£¼±µÈ°¡£¡
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Carbon-carbon bond activation reactions of asymmetric acetylene derivatives of the type L2Pt-(PhCÈýCR) were studied with 1,2-bis(diisopropylphosphino)ethane (dippe), 1,2-bis(di-tert-butyl-phosphino)ethane (dtbpe), and 1-iisopropylphosphino-2-dimethylaminoethane (dippdmae) chelates. (dippe)Pt(¦Ç2-PhCÈýCCH3)(1a), (dippe)Pt(¦Ç2-PhCÈýCCF3)(1b), and (dippe)Pt(¦Ç2-PhCÈýCC-(CH3)3)(1c) showed no thermal reactivity at 160 C, but 1b showed evidence for C-C cleavage to form (dippe)Pt(Ph)(CÈýCCF3) upon irradiation with UV light (>300 nm). In comparison, dtbpe analogues of thesemetal complexes, (dtbpe)Pt(¦Ç2-PhCÈýCCH3)(2a), (dtbpe)Pt(¦Ç2-PhCÈýCCF3)(2b),and (dtbpe)Pt(¦Ç2-PhCÈýCC(CH3)3)(2c), showed either C-HorC-C activation products upon photolysis. 2b produced (dtbpe)Pt(Ph)(CÈýCCF3), but 2a or 2c showed the formation of (dtbpe)Pt(D)(C6D5)(2D) by activation of the C6D6 solvent. Compounds 2a-c showed no thermal reactivity at 160 C. Two complexes with the hemilabile chelate dippdmae were synthesized and fully characterized, (dippdmae)Pt(¦Ç2-PhCÈýCCF3)(3b) and (dippdmae)Pt(¦Ç2-PhCÈýCC(CH3)3)(3c).C-C cleavage products of the type (L2)Pt(Ph)(CÈýCCF3) were observed only upon photolysis of compounds 1b, 2b, and 3b.
3Â¥2009-12-03 16:00:10
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