Thallium(I) Sandwich, Multidecker, and Ether Complexes Stabilized by Weakly-Coordinating Anions: A Spectroscopic, Structural, and Theoretical Investigation
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- 作者：Yann Sarazin ; David L. Hughes ; Nikolas Kaltsoyannis ; Joseph A. Wright ; and ; Manfred Bochmann
- 刊名：Journal of the American Chemical Society
- 出版年：2007
- 出版时间：January 31, 2007
- 年：2007
- 卷：129
- 期：4
- 页码：881 - 894
- 全文大小：465K
- 年卷期：v.129,no.4(January 31, 2007)
- ISSN：1520-5126
文摘
The reaction of thallium ethoxide with [H(OEt2)2][H2N{B(C6F5)3}2] in diethyl ether afforded [Tl(OEt2)3][H2N{B(C6F5)3}2] (2a), [Tl(OEt2)4][H2N{B(C6F5)3}2] (2b), or [Tl(OEt2)2][H2N{B(C6F5)3}2]·CH2Cl2 (2c),depending on the reaction conditions. The dication in the hydrolysis product [Tl4(
3-OH)2][H2N{B(C6F5)3}2]2·4CH2Cl2 consists of two bridging and two terminal Tl+ ions bound to triply bridging hydroxides. HeatingEt2O complexes in toluene afforded [Tl(
6-toluene)n][H2N{B(C6F5)3}2] (4, n = 2, 3), while C6Me6 additiongave the first thallium-C6Me6 adduct, [Tl(6-C6Me6)2][H2N{B(C6F5)3}2]·1.5CH2Cl2 (5a), a bent sandwichcomplex with very short Tl···centroid distances. These arene complexes show no close contacts betweencations and anions. Displacement of toluene ligands by ferrocene gave [Tl2(FeCp2)3][H2N{B(C6F5)3}2]2·5CH2Cl2 (6) which contains the multidecker cations [Tl(FeCp2)]+ and [Tl(FeCp2)2]+ in a 1:1 ratio. By contrast,decamethylferrocene leads to electron transfer; the isolable thallium-ferrocene complexes may thereforebe viewed as precursor complexes for this redox step. With 18-crown-6 the complexes [Tl(18-crown-6)2][H2N{B(C6F5)3}2] (11a) and [Tl(18-crown-6)][H2N{B(C6F5)3}2]·2CH2Cl2 (11b) were isolated. The structureof the latter shows an eight-coordinate thallium ion, where the coordination to the six oxygen donors inequatorial positions is completed by axial contacts to two F atoms of the counter anions. The bondingbetween thallium(I) and arenes was explored by density-functional theory (DFT) calculations. The optimizedgeometry of [Tl(tol)3]+ converged to a structure very similar to that obtained experimentally. Calculationson [Tl(C6Me6)2]+ (5b) to establish whether a linear or bent geometry is the most stable revealed a very flatpotential-energy surface for distortions of the Ctr(3)-Tl-Ctr(4) angle. Overall, there is very little energeticpreference for one particular geometry over another above about 140
, in good agreement with thecrystallographic geometry. The calculated Tl-arene interaction energies increase from 73.7 kJ mol-1 fortoluene to 121.7 kJ mol-1 for C6Me6.
3-OH)2][H2N{B(C6F5)3}2]2·4CH2Cl2 consists of two bridging and two terminal Tl+ ions bound to triply bridging hydroxides. HeatingEt2O complexes in toluene afforded [Tl(6-toluene)n][H2N{B(C6F5)3}2] (4, n = 2, 3), while C6Me6 additiongave the first thallium-C6Me6 adduct, [Tl(6-C6Me6)2][H2N{B(C6F5)3}2]·1.5CH2Cl2 (5a), a bent sandwichcomplex with very short Tl···centroid distances. These arene complexes show no close contacts betweencations and anions. Displacement of toluene ligands by ferrocene gave [Tl2(FeCp2)3][H2N{B(C6F5)3}2]2·5CH2Cl2 (6) which contains the multidecker cations [Tl(FeCp2)]+ and [Tl(FeCp2)2]+ in a 1:1 ratio. By contrast,decamethylferrocene leads to electron transfer; the isolable thallium-ferrocene complexes may thereforebe viewed as precursor complexes for this redox step. With 18-crown-6 the complexes [Tl(18-crown-6)2][H2N{B(C6F5)3}2] (11a) and [Tl(18-crown-6)][H2N{B(C6F5)3}2]·2CH2Cl2 (11b) were isolated. The structureof the latter shows an eight-coordinate thallium ion, where the coordination to the six oxygen donors inequatorial positions is completed by axial contacts to two F atoms of the counter anions. The bondingbetween thallium(I) and arenes was explored by density-functional theory (DFT) calculations. The optimizedgeometry of [Tl(tol)3]+ converged to a structure very similar to that obtained experimentally. Calculationson [Tl(C6Me6)2]+ (5b) to establish whether a linear or bent geometry is the most stable revealed a very flatpotential-energy surface for distortions of the Ctr(3)-Tl-Ctr(4) angle. Overall, there is very little energeticpreference for one particular geometry over another above about 140, in good agreement with thecrystallographic geometry. The calculated Tl-arene interaction energies increase from 73.7 kJ mol-1 fortoluene to 121.7 kJ mol-1 for C6Me6.