含主族元素(Bi、Te)與過渡金屬(Mo、Ru)團簇化合物的合成與化性研究

Abstract

1. Bi-Mo-CO系統

將NaBiO3與Mo(CO)6以莫耳比為1：1的比例於MeOC2H4OH中加熱迴流反應，可得到主體結構為四面體的化合物[Bu4N][BiMo3(CO)9(-OC2H4OMe)3Na]。

此化合物可與正一價或正二價陽離子做離子交換反應得到一系列相似結構之產物[BiMo3(CO)9(-OC2H4OMe)3ML]- (ML = Li，Tl，Ca(NCMe)2，Ca(OAc)，Pb(NO3)，ZnCl，Cd(OAc)，HgCl2，CoCl)。有趣的是當[BiMo3(CO)9(-OC2H4OMe)3Na]-加入KCl時卻無法反應，可能是立體障礙造成的結果。此外[BiMo3(CO)9(-OC2H4OMe)3Na]-與Pb(OAc)2反應時則可得到dimer形式的產物。同時我們進一步利用理論計算來佐證實驗中所得到的結果。

2. Te-Ru-CO系統

將K2TeO3與Ru3(CO)12以莫耳比為1：1的比例於MeOH中加熱迴流反應，可得到主體結構為八面體的化合物[PPh4]2[TeRu5(CO)14]•CH2Cl2。利用[PPh4]2[TeRu5(CO)14]•CH2Cl2與CuX (X = Cl，Br，I)反應，依不同比例可生成一系列含銅的新穎化合物：[TeRu5(CO)14CuX]2-、[TeRu5(CO)14Cu2X2]2-、[Te2Ru10(CO)28Cu4X2]2-與[Te2Ru4(CO)10Cu2X2]2-，並探討相互間的轉換關係，此外，我們亦利用理論計算來探討其相關的性質。

1. Bi-Mo-CO system

When NaBiO3 was treated with 1 equiv of Mo(CO)6 in a methanol solution, the novel tetrahedral cluster [BiMo3(CO)9(-OC2H4OMe)3Na]- was formed. [BiMo3(CO)9(-OC2H4OMe)3Na]- was found to undergo ion exchange with cations or dications to give the corresponding clusters [BiMo3(CO)9(-OC2H4OMe)3ML]- (ML = Li, Tl, Ca(NCMe)2, Ca(OAc), Pb(NO3), ZnCl, Cd(OAc), HgCl2, and CoCl). Interestingly, the ion exchange reaction of [BiMo3(CO)9(-OC2H4OMe)3Na]- with KCl was not observed probably due to the size effect, which was further supported by DFT calculations. In addition, further reaction of [BiMo3(CO)9(-OC2H4OMe)3Na]- with Pb(OAc)2 gave the dimeric complex rather than monomer species, which was also demonstrated by DFT calculations.

2. Te-Ru-CO system

The reaction of K2TeO3 with Ru3(CO)12 in a molar ratio of 1: 1 in a methanol solution produced an octahedral cluster [TeRu5(CO)14]2-. When [TeRu5(CO)14]2- was treated with CuX (X = Cl, Br, I) in various ratios, a series of copper-incorporated polynuclear complexes, [TeRu5(CO)14CuX]2-, [TeRu5(CO)14Cu2X2]2-, [Te2Ru10(CO)28Cu4X2]2-, and [Te2Ru4(CO)10Cu2X2]2- were synthesized. The transformation and the nature of these complexes were further studied and compared by DFT calculations.