Thallophilic Interactions in Aryloxide Compounds: the {Tl2(2-OAr)4} Structural Motif in (TlOAr)4
详细信息 查看全文
- 作者：Montana V. Childress ; David Millar ; Todd M. Alam ; Kevin A. Kreisel ; Glenn P. A. Yap ; Lev N. Zakharov ; James A. Golen ; Arnold L. Rheingold ; and Linda H. Doerrer
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：May 15, 2006
- 年：2006
- 卷：45
- 期：10
- 页码：3864 - 3877
- 全文大小：850K
- 年卷期：v.45,no.10(May 15, 2006)
- ISSN：1520-510X
文摘
Two thallium aryloxide compounds TlOC6F5 (TlOArF) and bis-3,5-TlOC6H3(CF3)2 (TlOAr') have been recrystallizedfrom THF and crystallographically characterized in different isomeric forms. The latter compound forms a solvatedtetrameric cubane, {TlOAr'}4·THF, 1. The TlOArF compound crystallized with a similar stoichiometry, {TlOArF}4·2THF, 2, but contains a {Tl2(
2-OArF)4} unit that includes a thallophilic interaction at a distance of 3.5943(15) Å.Solution 205Tl and 203Tl NMR studies of 1 and 2 support the retention of a cubane structure for 1 in solution andsuggest a similar structure for 2 with coupled thallium centers down to -90 
C. Fluorescence spectroscopy datafor both compounds 1 and 2 in THF are consistent with LMCT. DFT calculations of 1, 2, and three models of the{Tl2(2-OArF)4} unit show a bonding overlap of the bridged thallium atoms in 2 and are also used to describe thebonding in 1. The structures of two heterobimetallic compounds, Tl2Cu(OArF)4, 4, and Tl2Cu(OAr')4, 5, with the{Tl2(2-OArF)4} structural motif and thallophilic contacts of 3.86(6) and 3.564(1) Å, respectively, are described. Thecrystal structures of the unsolvated of TlOArF, 2b, solvated heterobimetallic derivative Tl2Cu(OAr')4·2THF, 5b, andthe monomeric (18-crown-6)TlOArF, 3, and 205Tl NMR spectra of TlOC6H5, 6, are also reported for comparisonpurposes.
2-OArF)4} unit that includes a thallophilic interaction at a distance of 3.5943(15) Å.Solution 205Tl and 203Tl NMR studies of 1 and 2 support the retention of a cubane structure for 1 in solution andsuggest a similar structure for 2 with coupled thallium centers down to -90 C. Fluorescence spectroscopy datafor both compounds 1 and 2 in THF are consistent with LMCT. DFT calculations of 1, 2, and three models of the{Tl2(2-OArF)4} unit show a bonding overlap of the bridged thallium atoms in 2 and are also used to describe thebonding in 1. The structures of two heterobimetallic compounds, Tl2Cu(OArF)4, 4, and Tl2Cu(OAr')4, 5, with the{Tl2(2-OArF)4} structural motif and thallophilic contacts of 3.86(6) and 3.564(1) Å, respectively, are described. Thecrystal structures of the unsolvated of TlOArF, 2b, solvated heterobimetallic derivative Tl2Cu(OAr')4·2THF, 5b, andthe monomeric (18-crown-6)TlOArF, 3, and 205Tl NMR spectra of TlOC6H5, 6, are also reported for comparisonpurposes.