Diruthenium Naphthalene and Anthracene Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand
详细信息 查看全文
- 作者：H茅lori Salembier ; Joshua Mauldin ; Tom Hammond ; Rodney Wallace ; Essa Alqassab ; Michael B. Hall ; Lisa M. P茅rez ; Yuen-Jing Alexis Chen ; Katherine E. Turner ; Eric Bockoven ; William Brennessel ; Robert M. Chin
- 刊名：Organometallics
- 出版年：2012
- 出版时间：July 9, 2012
- 年：2012
- 卷：31
- 期：13
- 页码：4838-4848
- 全文大小：587K
- 年卷期：v.31,no.13(July 9, 2012)
- ISSN：1520-6041
文摘
The reaction of cis-{(畏5-C5H3)2(CMe2)2}Ru2(CO)4Br2 with naphthalene affords the syn-facial [cis-{(畏5-C5H3)2(CMe2)2}Ru2(渭-畏6,畏6-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鈥搈etal bond and sharing electrons from the central 蟺 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 畏6 to 畏4 on one of the naphthalene rings and yields cis-{(畏5-C5H3)2(CMe2)2}Ru2(渭-畏6,畏4-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-{(畏5-C5H3)2(CMe2)2}Ru2(CO)4Br2 with anthracene affords the analogous syn-facial anthracene complex, [cis-{(畏5-C5H3)2(CMe2)2}Ru2(渭-畏6,畏6-C14H10)][OTf]2, (4), and the tetranuclear dianthracene complex, [cis-{(畏5-C5H3)2(CMe2)2}Ru2(渭-畏6,畏6-C14H10)]2[OTf]4, (5). 22+, 20, and 5 were structurally characterized by X-ray diffraction.