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monanfang04Ìú³æ (³õÈëÎÄ̳)
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Many transition metal complexes reactwith carbon dioxide.Carbon dioxide is activated by transition metals and forms complexes having bent bond structures and longer bond lengths, e.g. in Ni(CO2)(P(C6H11)3)2Ph-CH3: C¨CO¨CC bond angle is changed from 1808 to 1338 and C¨CO bond lengths is changed from1.16 to 1.22 A ¡ã and 1.17 A ¡ã as shown in Fig. 3 [8]. On the other hand, carbon¨Ccarbon unsaturated compounds such as monoolefins, dienes, allenes and acetylenes react also with transition metal complexes to form their metal pcomplexes. Both carbon dioxide and these carbon¨Ccarbon unsaturated compounds bond with the same transition metal and they are activated. Therefore, carbon dioxide is able to react with the carbon¨C carbon unsaturated compounds such as alkynes, conjugated dienes and allenes in the presence of transition metal compounds as the catalysts to yield six-membered unsaturated lactones (Eqs. (24)¨C(26)) or five-membered metalalactone (Eq. (27)) [143¨C145] In the cyclic addition of diynes (RCBBC¨C(CH2)m-CBBCR) with carbon dioxide in the presence of a zero valent nickel catalyst, the reaction with m = 3 or 4, easily proceeds to give two cyclic 2-pyrones in about 50¨C90% yields as shown in Eq. (28). However, the reaction with m 2 and m 6, the alternating copolymerization of the diynes and carbon dioxide proceeds to give a poly(2-pyrone) by an intermolecular cycloaddition, since the intramolecular cycloaddition reaction is difficult as shown in Eqs. (29) and (30) [150a,150b]. The reactions of these diynes and carbon dioxide in the presence of metal compounds gave the various kinds of polymeric compounds, e.g., an alternating copolymer as shown in Eq. (31) [145,150c,150d] |
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monanfang04: ½ð±Ò+45, ·ÒëEPI+1, ¡ï¡ï¡ï¡ï¡ï×î¼Ñ´ð°¸ 2013-04-29 19:08:00
monanfang04: ½ð±Ò+45, ·ÒëEPI+1, ¡ï¡ï¡ï¡ï¡ï×î¼Ñ´ð°¸ 2013-04-29 19:08:00
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Many transition metal complexes react with carbon dioxide. Carbon dioxide is activated by transition metals and forms complexes having bent bond structures and longer bond lengths, e.g. in Ni(CO2)(P(C6H11)3)2Ph-CH3: C¨CO¨CC bond angle is changed from 1808 to 1338 and C¨CO bond lengths is changed from1.16 to 1.22 A ¡ã and 1.17 A ¡ã as shown in Fig. 3 [8]. On the other hand, carbon¨Ccarbon unsaturated compounds such as monoolefins, dienes, allenes and acetylenes react also with transition metal complexes to form their metal pcomplexes. ºÜ¶à¹ý¶É½ðÊôÅäºÏÎï¿ÉÒÔÓë¶þÑõ»¯Ì¼·´Ó¦¡£¹ý¶É½ðÊô»î»¯¶þÑõ»¯Ì¼ÒÔºóÐγɵÄÅäºÏÎï¾ßÓÐÍäÇú¼ü£¬¼ü³¤½Ï³¤£¬±ÈÈ磺Ni(CO2)(P(C6H11)3)2Ph-CH3ÅäºÏÎïÖÐC¨CO¨CC¼ü½ÇÓÉ180¡ã±äΪ133¡ã£¬²¢ÇÒ̼Ñõ¼ü³¤ÓÉ1.16 A¡ã£¨0.1nm£©±äΪ1.22ºÍ1.17 A¡ã£¬¼ûͼ3[8]¡£ÁíÒ»·½Ã棬̼̼²»±¥ºÍ»¯ºÏÎ±ÈÈ磺µ¥Ï©Ìþ¡¢¶þÏ©Ìþ¡¢±û¶þÏ©ºÍÒÒȲҲ¿ÉÒÔÓë¹ý¶É½ðÊôÅäºÏÎï·´Ó¦ÐγɶÔÓ¦½ðÊôµÄÅäºÏÌ壨pcomplexes£©¡£ Both carbon dioxide and these carbon¨Ccarbon unsaturated compounds bond with the same transition metal and they are activated. Therefore, carbon dioxide is able to react with the carbon¨Ccarbon unsaturated compounds such as alkynes, conjugated dienes and allenes in the presence of transition metal compounds as the catalysts to yield six-membered unsaturated lactones (Eqs. (24)¨C(26)) or five-membered metalalactone (Eq. (27)) [143¨C145]. ÔÚ¹ý¶É½ðÊô´æÔÚµÄÌõ¼þÏ£¬¶þÑõ»¯Ì¼ºÍÕâЩ̼̼²»±¥ºÍ»¯ºÏÎïµÄ¼ü¶¼»á±»»î»¯¡£Îª´Ë£¬ÔÚ¹ý¶É½ðÊô»¯ºÏÎï×÷Ϊ´ß»¯¼Á´æÔÚµÄÌõ¼þÏ£¬¶þÑõ»¯Ì¼¿ÉÒÔÓë̼̼²»±¥ºÍ»¯ºÏÎï·´Ó¦£¬±ÈÈ磺ȲÌþ,¹²éî¶þÏ©ÌþºÍ±û¶þÏ©£¬»á²úÉúÁùÔª²»±¥ºÍÄÚõ¥£¨Eqs. (24)¨C(26)£©»òÕßÎåÔª½ðÊô»¯ÂÝÐýÄÚõ¥£¨Eq. (27)£©[143¨C145]¡£ In the cyclic addition of diynes (RCBBC¨C(CH2)m-CBBCR) with carbon dioxide in the presence of a zero valent nickel catalyst, the reaction with m = 3 or 4, easily proceeds to give two cyclic 2-pyrones in about 50¨C90% yields as shown in Eq. (28). However, the reaction with m = 2 and m = 6, the alternating copolymerization of the diynes and carbon dioxide proceeds to give a poly(2-pyrone) by an intermolecular cycloaddition, since the intramolecular cycloaddition reaction is difficult as shown in Eqs. (29) and (30) [150a,150b]. The reactions of these diynes and carbon dioxide in the presence of metal compounds gave the various kinds of polymeric compounds, e.g., an alternating copolymer as shown in Eq. (31) [145,150c,150d] ÔÚÄøµ¥ÖÊ£¨0»¯ºÏ¼Û£©×÷Ϊ´ß»¯¼ÁµÄÌõ¼þÏ£¬ÅäλΪ3»òÕß4£¬Ñ»·¼ÓÈë¶þȲÌþ£¨RCBBC¨C(CH2)m-CBBCR£©ÒÔ¼°¶þÑõ»¯Ì¼£¬ºÜÈÝÒ×·´Ó¦Éú³É¶þÔªßÁà«Íª£¨two cyclic 2-pyrones£©£¬²úÁ¿Îª50%-90%£¬·´Ó¦¹ý³Ì¼ûEq. (28)¡£È»¶ø£¬ÓÉÓÚ·Ö×Ӽ价¼Ó³É·´Ó¦ÊǷdz£ÄÑÒÔ½øÐеģ¬ÅäλΪ2»òÕß6ʱ£¬¶þȲÌþºÍ¶þÑõ»¯Ì¼µÄ½»Ìæ¹²¾Û×÷Óûáͨ¹ý·Ö×Ӽ价¼Ó³É·´Ó¦²úÉú¶à¾Û(2ßÁà«Íª)¡£¼û·´Ó¦(29)ºÍ(30) [150a,150b]¡£ÔÚ½ðÊôÅäºÏÎï´æÔÚµÄÌõ¼þÏ£¬ÕâЩ¶þȲÌþÓë¶þÑõ»¯Ì¼µÄ·´Ó¦»á²úÉú¸÷Öָ߷Ö×Ó¾ÛºÏÎ±ÈÈ磺°´·´Ó¦(31) [145,150c,150d]²úÉúµÄ½»Ìæ¹²¾ÛÎï¡£ |
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