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monanfang04鐵蟲 (初入文壇)
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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–O–C bond angle is changed from 1808 to 1338 and C–O bond lengths is changed from1.16 to 1.22 A ° and 1.17 A ° as shown in Fig. 3 [8]. On the other hand, carbon–carbon 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–carbon unsaturated compounds bond with the same transition metal and they are activated. Therefore, carbon dioxide is able to react with the carbon– 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)–(26)) or five-membered metalalactone (Eq. (27)) [143–145] In the cyclic addition of diynes (RCBBC–(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 50–90% 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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huangzx1314
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monanfang04: 金幣+45, 翻譯EPI+1, ★★★★★最佳答案 2013-04-29 19:08:00
monanfang04: 金幣+45, 翻譯EPI+1, ★★★★★最佳答案 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–O–C bond angle is changed from 1808 to 1338 and C–O bond lengths is changed from1.16 to 1.22 A ° and 1.17 A ° as shown in Fig. 3 [8]. On the other hand, carbon–carbon unsaturated compounds such as monoolefins, dienes, allenes and acetylenes react also with transition metal complexes to form their metal pcomplexes. 很多過渡金屬配合物可以與二氧化碳反應(yīng)。過渡金屬活化二氧化碳以后形成的配合物具有彎曲鍵，鍵長較長，比如：Ni(CO2)(P(C6H11)3)2Ph-CH3配合物中C–O–C鍵角由180°變?yōu)?33°，并且碳氧鍵長由1.16 A°（0.1nm）變?yōu)?.22和1.17 A°，見圖3[8]。另一方面，碳碳不飽和化合物，比如：單烯烴、二烯烴、丙二烯和乙炔也可以與過渡金屬配合物反應(yīng)形成對應(yīng)金屬的配合體（pcomplexes）。 Both carbon dioxide and these carbon–carbon unsaturated compounds bond with the same transition metal and they are activated. Therefore, carbon dioxide is able to react with the carbon–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)–(26)) or five-membered metalalactone (Eq. (27)) [143–145]. 在過渡金屬存在的條件下，二氧化碳和這些碳碳不飽和化合物的鍵都會被活化。為此，在過渡金屬化合物作為催化劑存在的條件下，二氧化碳可以與碳碳不飽和化合物反應(yīng)，比如：炔烴,共軛二烯烴和丙二烯，會產(chǎn)生六元不飽和內(nèi)酯（Eqs. (24)–(26)）或者五元金屬化螺旋內(nèi)酯（Eq. (27)）[143–145]。 In the cyclic addition of diynes (RCBBC–(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 50–90% 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] 在鎳單質(zhì)（0化合價）作為催化劑的條件下，配位為3或者4，循環(huán)加入二炔烴（RCBBC–(CH2)m-CBBCR）以及二氧化碳，很容易反應(yīng)生成二元吡喃酮（two cyclic 2-pyrones），產(chǎn)量為50%-90%，反應(yīng)過程見Eq. (28)。然而，由于分子間環(huán)加成反應(yīng)是非常難以進行的，配位為2或者6時，二炔烴和二氧化碳的交替共聚作用會通過分子間環(huán)加成反應(yīng)產(chǎn)生多聚(2吡喃酮)。見反應(yīng)(29)和(30) [150a,150b]。在金屬配合物存在的條件下，這些二炔烴與二氧化碳的反應(yīng)會產(chǎn)生各種高分子聚合物，比如：按反應(yīng)(31) [145,150c,150d]產(chǎn)生的交替共聚物。 |
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