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北京石油化工学院2026年研究生招生接收调剂公告
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monanfang04

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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: 金币+45, 翻译EPI+1, ★★★★★最佳答案 2013-04-29 19:08:00
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.

很多过渡金属配合物可以与二氧化碳反应。过渡金属活化二氧化碳以后形成的配合物具有弯曲键,键长较长,比如:Ni(CO2)(P(C6H11)3)2Ph-CH3配合物中C–O–C键角由180°变为133°,并且碳氧键长由1.16 A°(0.1nm)变为1.22和1.17 A°,见图3[8]。另一方面,碳碳不饱和化合物,比如:单烯烃、二烯烃、丙二烯和乙炔也可以与过渡金属配合物反应形成对应金属的配合体(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].

在过渡金属存在的条件下,二氧化碳和这些碳碳不饱和化合物的键都会被活化。为此,在过渡金属化合物作为催化剂存在的条件下,二氧化碳可以与碳碳不饱和化合物反应,比如:炔烃,共轭二烯烃和丙二烯,会产生六元不饱和内酯(Eqs. (24)–(26))或者五元金属化螺旋内酯(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]

在镍单质(0化合价)作为催化剂的条件下,配位为3或者4,循环加入二炔烃(RCBBC–(CH2)m-CBBCR)以及二氧化碳,很容易反应生成二元吡喃酮(two cyclic 2-pyrones),产量为50%-90%,反应过程见Eq. (28)。然而,由于分子间环加成反应是非常难以进行的,配位为2或者6时,二炔烃和二氧化碳的交替共聚作用会通过分子间环加成反应产生多聚(2吡喃酮)。见反应(29)和(30) [150a,150b]。在金属配合物存在的条件下,这些二炔烃与二氧化碳的反应会产生各种高分子聚合物,比如:按反应(31) [145,150c,150d]产生的交替共聚物。
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