期刊
DALTON TRANSACTIONS
卷 42, 期 37, 页码 13349-13356出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3dt32872d
关键词
-
资金
- Alexander von Humboldt Foundation
DFT calculations using BP86 in conjunction with the SVP and TZVPP basis sets as well as ab initio calculations at SCS-MP2 have been carried out for six dicoordinated carbon molecules CLL' where L is a fluorenyl carbene while L' is a phosphine PH3 (1) or PPh3 (2) or a carbene, i.e. NHCMe (3), benzannulated NHCMe (4), cycloheptatrienylidene (5) and benzannulated cycloheptatrienylidene (6). The complexes of these compounds with one and two AuCl moieties were also calculated. The monoaurated adducts of 1-4 have the AuCl fragment eta(1) coordinated to the central carbon atom. The complexes 5(AuCl) and 6(AuCl) have AuCl eta(2) bonded across a C=C double bond. Three different bonding modes are found as energy minima for the diaurated species LL'C-(AuCl)(2). The AuCl fragments are found to be either both coordinated eta(1), both coordinated eta(2) across double bonds, or a combination of the two. According to the electronic structure analysis of the free compounds, 1 and 2 might best be classified as carbenes, 3 and 4 as bent allenes while 5 and 6 are typical allenes. The complexation with AuCl reveals that 1-4 may exhibit chemical behaviour which is typical for carbones and thus, they may be termed hidden carbones. The AuCl complexes show that compounds 5 and 6 are classical allenes.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据