第十六族碲與過渡金屬(Cr、Mo、Mn)金屬團簇化合物之合成與化性和物性研究

陳佩琪(Pei-Qi Chen)

指導教授 ： 謝明惠

國立臺灣師範大學/理學院/化學系/碩士(2006年)

摘要

[1] 碲(Te)-鉻(Cr)系統的研究
將 [Te{Cr(CO)5}3]2-與HBF4或O2反應，會迅速反應生成已知的平面型化合物 [Te2{Cr(CO)5}4]2- (1)，而與有機試劑ClH2C(C6H4)2CH2Cl反應則可得到新的雙聚合化合物 [H2C(C6H4)2CH2Te2{Cr(CO)5}6]2- (2)。利用 HgCl2 分別與 [Te{Cr(CO)5}n]2- (n = 2, 3) 進行反應，可成功合成出以汞橋接之雙聚合金屬團簇化合物 [HgTe2{Cr(CO)5}n] 2- (n = 6, (3); n = 4, (4))，化合物 3 亦可藉由化合物 4 與 HgCl2 試劑反應而獲得。將 [Te{Cr(CO)5}3]2- 更進一步與 Se powder反應，可成功得到一開放型結構化合物 [SeTe{Cr(CO)5}3]2- (6)。此外，我們針對新的化合物與相關的化合物做一系列的比較，並藉由分子軌域理論計算更深入探討其結果。

[2] 碲(Te)-鉻(Cr)-錳(Mn)系統的研究
將化合物 [Te2Cr2Mn2(CO)18]2- (7) 於鹼性丙酮與甲醇混合溶劑中，加熱迴流，可得一特殊混合鉻-錳金屬雙三角錐化合物[Te2CrMn2(CO)9]2- (8)。將化合物8 與 CO氣體於室溫下反應，可得到四角錐封閉型結構化合物 [Te2CrMn2(CO)10]2- (9)。化合物 9 於二氯甲烷溶劑下加熱迴流則進行逆反應而得到化合物 8。化合物8與 O2 氣體在二氯甲烷室溫下反應可生成化合物 9。將Cu(MeCN)4BF4 試劑與化合物 9 反應則得到化合物 8。此二化合物均符合18電子計算規則，然而經由SQUID磁性測量可發現，於室溫 (300 K) 時均呈現S = 1，即具有2個不成對電子，顯示出反鐵磁 (antiferromagnetism) 的現象。另外，我們也利用DFT理論計算來探討此現象。

[3] 碲(Te)-鉬(Mo)系統的研究
將 [Te2Cr3(CO)10]2- (10) 和Mo(CO)6的丙酮溶液加熱反應，不同的反應時間，可得到不同的結果：與4當量的Mo(CO)6 加熱反應2天，可得到包含2個hydride主結構為四面體新型化合物 [H2Te2Mo4(CO)12]2- (11)；將反應時間縮短至1小時，則可得到開放結構混合金屬鉻、鉬新的化合物 [Te2CrMo3(CO)18]2- (12)；將反應時間縮短至30分鐘，得到一已知開放結構化合物 [Te2Cr2Mo2(CO)18]2- (13)。將化合物 13 與2當量的Mo(CO)6於丙酮溶液中加熱反應可得到化合物11。而化合物10與4當量的Mo(CO)6於室溫下反應14 天，僅可得到已知化合物 13。另外，我們也利用DFT理論計算來佐證與推測實驗的過程。

關鍵字

金屬團簇物

並列摘要

Abstract
[1] Te-Cr system
[Te{Cr(CO)5}3]2- rapidly transformed to the known dimeric open cluster [Te2{Cr(CO)5}4]2- (1) upon the reaction with HBF4 or O2 while the reaction with biphenyl-containing reagent ClH2C(C6H4)2CH2Cl produced the CH2(C6H4)2CH2-bridged dimeric complex [H2C(C6H4)2CH2Te2{Cr(CO)5}6]2- (2) was produced. The reaction of [Te{Cr(CO)5}n]2- (n = 2, 3) with HgCl2 afforded the dimeric Hg-bridged metal clusters [HgTe2{Cr(CO)5}n] 2- (n = 6, (3); n = 4, (4)), respectively. While [Te{Cr(CO)5}3]2- was treated with Se powder, a new open complex [SeTe{Cr(CO)5}3]2- (6) was obtained. Moreover, the new complexes and related reactions were investigated by molecular orbital calculations at the B3LYP level of the density functional theory.

[2] Te-Cr-Mn system
Refluxing [Te2Cr2Mn2(CO)18]2- (7) in a basic acetone/MeOH solution produced the mixed-metal closo-cluster complex [Te2CrMn2(CO)9]2- (8). A novel new square pyramidal cluster, [Te2CrMn2(CO)10]2- (9) could be obtained from the slow diffusion of CO into complex 8 in dichromethane solution. Conversely, complex 9 could reconvert back to complex 8 in refluxing dichromethane solution. When complex 8 was bubbled with O2 in dichromethane at room temperature, complex 9 could also be produced. Besides, complex 9 could react with Cu(MeCN)4BF4 to form complex 8. Interestingly, [Te2CrMn2(CO)9]2- (8) and [Te2CrMn2(CO)10]2- (9) are electron-precise species and each exhibt esceptionally antiferromagnetism properties with an S = 1 (2 unpaired electrons) configuration at 300 K by SQUID analysis. We further investigated the phenomenon by molecular orbital calculations at the B3LYP level of the density functional theory.

[3] Te-Mo system
The reaction of [Te2Cr3(CO)10]2- (10) with Mo(CO)6 in various reaction conditions was systematically studied. A novel new hydrido-tedrahedral cluster [H2Te2Mo4(CO)12]2- (11) was obtained from the reacion of complex 10 with 4 eq Mo(CO)6 in refluxing acetone solution for 2 days, in which the known open-cluster [Te2Cr2Mo2(CO)18]2- (13) and the new open mixed-metal cluster [Te2CrMo3(CO)18]2- (12) were isolated as intermediates by X-ray analyses. Further refluxing of complex 13 with 2 eq Mo(CO)6 in an acetone solution could lead to the formation of the new complex 11. However, the reaction of complex 10 with 4 eq Mo(CO)6 at room temperature for a prolonged time only formed the known complex 13. These reactions were further investigated by molecular orbital calculations at the B3LYP level of the density functional theory.

並列關鍵字

Te ； Mo ； Cr ； Mn

參考文獻

1. Adams, R. D.; Captain, B.; Fu, W.; Pellechia, P. J.; Smith, M. D. Angew. Chem. Int. Ed. Engl. 2002, 41, 1951.

3. Whitmire, K. H. J. Cluster Sci. 1991, 12, 231.

5. Riaz, U.; Cumow, O. J.; Curtis, M. D. J. Am. Chem. Soc. 1994, 116, 4357.

7. Dance, I. J. Chem. Soc., Chem. Commun. 2003, 324.

8. Chen, L.; Wu, X. T.; Gao, X. C.; Zhang, W. J.; Lin, P. J. Chem. Soc., Dalton Trans. 1999, 4303.