Synthesis and Reactivity of a Diruthenium Diazoalkane Complex
Synthesis and Reactivity of a Diruthenium Diazoalkane Complex
复制标题
二钌重氮烷配合物的合成和反应活性
DOI：
10.1021/om0102293
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发表时间：
2001
期刊：
影响因子：
2.8
通讯作者：
H. Jenkins
中科院分区：
文献类型：
--
作者：
Yuan Gao;M. Jennings;R. Puddephatt;H. Jenkins
[Ru2(μ-CO)(CO)4(μ-dppm)2],1, dppm = Ph2PCH2PPh2，与N2CHCO2Et反应得到配合物[Ru2(μ-NNCHCO2Et)(CO)4(μ-dppm)2],2，其中重氮烷烃作为新型的2电子配体桥接金属-金属键。配合物2与苯基乙炔反应，取代羰基配体，得到[Ru2(μ-CO)(CO)2{μ-NN(CHCO2Et)(CPhCH)}(μ-dppm)2],3a，其中含有重氮烷烃和炔配体在二钌中心偶联形成的新型金属环。质子首先攻击配合物2在NCH中心生成烷基重氮配合物[Ru2(CO)4(μ-NNCH2CO2Et)(μ-dppm)2]+,4，然后与强酸H[BF4]一起，在Ru−Ru键生成阳离子配合物[Ru2(μ-H)(CO)4(μ-NNCH2CO2Et)(μ-dppm)2]2+,5。络合物2是甲酸分解生成co2和H2的预催化剂，并描述了导致活性催化剂的化学反应。
Reaction of [Ru2(μ-CO)(CO)4(μ-dppm)2],1, dppm = Ph2PCH2PPh2, with N2CHCO2Et gives the complex [Ru2(μ-NNCHCO2Et)(CO)4(μ-dppm)2],2, in which the diazoalkane acts as a novel 2-electron ligand bridging a metal−metal bond. Complex2reacts with phenylacetylene, with displacement of a carbonyl ligand, to give [Ru2(μ-CO)(CO)2{μ-NN(CHCO2Et)(CPhCH)}(μ-dppm)2],3a, which contains a new type of metallacycle formed by coupling of the diazoalkane and alkyne ligands at the diruthenium center. Protons attack complex2first at the NCH center to give the alkyldiazonium complex [Ru2(CO)4(μ-NNCH2CO2Et)(μ-dppm)2]+,4, and then, with the strong acid H[BF4], at the Ru−Ru bond to give the dicationic complex [Ru2(μ-H)(CO)4(μ-NNCH2CO2Et)(μ-dppm)2]2+,5. Complex2is a precatalyst for the decomposition of formic acid to give CO2and H2, and the chemistry leading to the active catalyst is described.