Diruthenium Naphthalene and Anthracene Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand
Diruthenium Naphthalene and Anthracene Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand
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含有双联二环戊二烯基配体的二钌萘和蒽络合物
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发表时间：
2012
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通讯作者：
R. Chin
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作者：
H. Salembier;Joshua P. Mauldin;Tom Hammond;Rodney Wallace;Essa Alqassab;M. Hall;L. M. Pérez;Y. Chen;Katherine E. Turner;Eric Bockoven;W. Brennessel;R. Chin
cis-{（η5-C5 H3）2（CMe 2）2} Ru 2（CO）4 Br 2与萘反应，得到顺式[cis-{（η5-C5 H3）2（CMe 2）2} Ru 2（μ-η6，η6-C10 H8）][OTf]2，（22+），一个比18电子规则少两个电子的配合物。密度泛函理论（DFT）计算表明，Ru原子通过弱金属-金属键和共享来自萘中心π键的电子的组合来满足其缺失的价态。22+的单电子还原产生2+，一种II类混合价络合物，而22+的双电子还原导致萘环上的一个从η6到η4的hapticity变化，并产生cis-{（η5-C5 H3）2（CMe 2）2} Ru 2（μ-η6，η4-C10 H8）（20），一种两性离子络合物。DFT计算预测20的Cs异构体的能量比C2 v异构体低4.69 kcal/mol，C2 v异构体是过渡态。顺式-{（η5-C5 H3）2（CMe 2）2} Ru 2（CO）4 Br 2与蒽反应，得到类似的同面蒽配合物[cis-{（η5-C5 H3）2（CMe 2）2} Ru 2（μ-η6，η6-C14 H10）][OTf]2，（4）和（4）。
The reaction of cis-{(η5-C5H3)2(CMe2)2}Ru2(CO)4Br2 with naphthalene affords the syn-facial [cis-{(η5-C5H3)2(CMe2)2}Ru2(μ-η6,η6-C10H8)][OTf]2, (22+), a complex that appears to be two electrons short of the 18-electron rule. Density functional theory (DFT) calculations suggest that the Ru atoms satisfy their missing valence by a combination of a weak metal–metal bond and sharing electrons from the central π bond of the naphthalene. The one-electron reduction of 22+ yields 2+, a Class II mixed-valence complex, while the two-electron reduction of 22+ causes a hapticity change from η6 to η4 on one of the naphthalene rings and yields cis-{(η5-C5H3)2(CMe2)2}Ru2(μ-η6,η4-C10H8) (20), a zwitterionic complex. The DFT calculations predict that the Cs isomer of 20 is 4.69 kcal/mol lower in energy than the C2v isomer, which is a transition state. Reaction of cis-{(η5-C5H3)2(CMe2)2}Ru2(CO)4Br2 with anthracene affords the analogous syn-facial anthracene complex, [cis-{(η5-C5H3)2(CMe2)2}Ru2(μ-η6,η6-C14H10)][OTf]2, (4), an...