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首页> 外文期刊>Organometallics >Protonation and H-2 heterolysis reactions of electrophilic (eta(5)-C5R5)Ru(dfepe)(X) (R = H, Me; X = H, OTf) complexes
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Protonation and H-2 heterolysis reactions of electrophilic (eta(5)-C5R5)Ru(dfepe)(X) (R = H, Me; X = H, OTf) complexes

机译：亲电子（eta（5）-C5R5）Ru（dfepe）（X）（R = H，Me; X = H，OTf）配合物的质子化和H-2杂化反应

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Addition of excess HOSO2CF3 (HOTf) to CpRu(L)H (1) (L = dfepe = PR2CH2CH2PR2, R = C2F5) in CD2Cl2 under N-2 produces a mixture of [CpRu(L)(H)(2)](+) (2a), [CpRu(L)(H-2)](+) (2b), and CpRu(L)(OTf) (3) in a ratio of 1:5:2. Salts of the acid [HOEt2](+) are not strong enough to protonate 1. Complexes 2 slowly eliminate Hz to give 3; this reaction is slowed by-adding excess HOTf. Of all such complexes [CpRu(PR2CH2CH2PR2)(H-2)](+), R = alkyl and aryl, the dihydrogen complex 2b has the greatest acidity (similar to that of HOTf) and the related HD complex has the greatest J(HD) (29.1 Hz) because of the electron-withdrawing substituents R R = C2F5. The reaction of 3 with 1 atm H-2(g) proceeds much faster in the presence than in the absence of 1 equiv of HOTf to produce 1 and HOTf. This is a rare example of the production of a strong acid from H-2(g) where the intermediate dihydrogen complex has been characterized. Reaction of Cp*Ru(L)Cl (4), Cp* = C5Me5, in dry CH2Cl2 at -78 degrees C with AgX salts under H-2(g) (1 atm) gives mixtures of Cp*Ru(L)H (5) and [Cp*Ru(L)(H)(2)](+) (6), which have been identified by H-1 NMR. 6 is deprotonated by traces of water or by PPh3 to give Cp*Ru(L)H (5). The addition of excess HOTf mixtures of 5 and 6 under H-2(g) produces 6. Complexes 3, 4, and 5 have been characterized by single-crystal X-ray diffraction. Complexes CpRu(L)Cl, 1, 4, and 5 have very positive redox potentials that indicate that the dfepe ligand has the electron-withdrawing power close to that of two carbonyl ligands. [References: 52]
机译：在N-2下在CD2Cl2中将过量的HOSO2CF3（HOTf）添加到CpRu（L）H（1）（L = dfepe = PR2CH2CH2PR2，R = C2F5）产生[CpRu（L）（H）（2）]的混合物+）（2a），[CpRu（L）（H-2）]（+）（2b）和CpRu（L）（OTf）（3）的比例为1：5：2。酸[HOEt2]（+）的盐不足以使1质子化。络合物2缓慢消除Hz，得到3。加入过量的HOTf会减慢该反应。在所有此类配合物[CpRu（PR2CH2CH2PR2）（H-2）]（+）中，R =烷基和芳基，二氢配合物2b具有最大的酸度（类似于HOTf），相关的HD配合物具有最大的J（ HD（29.1 Hz），因为吸电子取代基RR = C2F5。 3与1 atm H-2（g）的反应比有1当量的HOTf产生1和HOTf的反应快得多。这是从H-2（g）生产强酸的罕见实例，其中已表征了中间体二氢络合物。 Cp * Ru（L）Cl（4）（Cp * = C5Me5）在干燥的CH2Cl2中于-78摄氏度下与AgX盐在H-2（g）（1 atm）下反应，得到Cp * Ru（L）H的混合物（5）和[Cp * Ru（L）（H）（2）]（+）（6），已通过H-1 NMR鉴定。用痕量水或PPh3使6脱质子，得到Cp * Ru（L）H（5）。在H-2（g）下加入过量的5和6的HOTf混合物会生成6。配合物3、4和5已通过单晶X射线衍射表征。配合物CpRu（L）Cl，1、4和5具有非常正的氧化还原电势，表明dfepe配体的吸电子能力接近两个羰基配体。 [参考：52]

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