含十六族元素與過渡金屬(鉻、錳、釕)團簇化合物的合成與其反應探討及化性研究
Abstract
中文摘要
1. Se-Ru-CuCl 系統
以[SeRu5(CO)14]2−為起始物，與不同當量CuCl進行反應，改變反應溫度與溶劑可得一系列單銅[SeRu5(CO)14CuCl]2− 、雙銅[SeRu5(CO)14(CuCl)2]2− 與四銅[Se2Ru10(CO)28Cu4Cl2]2−的新穎化合物，逐漸增大結構，進而得到最終重組性產物[Se2Ru4(CO)10Cu2Cl2]2−。
若以[SeRu5(CO)14CuCl]2−為起始物，再加入一當量的CuCl，亦可得到四銅[Se2Ru10(CO)28Cu4Cl2]2−與對稱結構[Se2Ru4(CO)10Cu2Cl2]2−，證實了結構與結構間的轉換關係；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. E-Cr-Mn (E = S, Se )系統
過去本實驗室在Te-Cr-Mn系統，藉由CO的加入可以將雙三角錐化合物[PPN]2[Te2CrMn2(CO)9]轉變成金字塔型化合物[PPN]2[Te2CrMn2(CO)10]；然而在E-Cr-Mn (E = S, Se) 系統方面，有相同tbp結構的[PPN]2[E2CrMn2(CO)9] (E = S, Se)，卻無法進行類似的CO加成反應，得到類似的化合物；我們以理論計算的結果來輔助證明實驗結果。此外我們可以藉由一鍋化一步合成直接得到大量[PPN]2[Te2CrMn2(CO)9]的前驅物[PPN]2 [Te2Cr2Mn2(CO)18]，節省了大量的人力及物力。
3. Se-Mn系統
以[Se2Mn3(CO)9]−為主體與異核金屬Cr(CO)6以1：1的莫耳數在4M的KOH甲醇溶液下反應，隨著反應時間的加長，可依序得到水瓢狀產物[HSe2CrMn3(CO)14]2−及八面體結構化合物[Se2CrMn3(CO)12]3−；過去由於分離困難且需長時間反應，現在我們改變反應條件，可以在短時間拿到較大量的化合物，並解決了分離上的困難
將[HSe2CrMn3(CO)14]2−與外加的Cr(CO)6在CH2Cl2溶液中加熱回流反應，可在未與-Cr(CO)5鍵結的Se接上另一個-Cr(CO)5的片段，形成一對稱結構的化合物[HSe2Cr2Mn3(CO)19]2−；[HSe2Cr2Mn3(CO)19]2−亦可藉由通入CO，在THF溶液下反應變回[HSe2CrMn3(CO)14]2−，兩者間具有轉變的機制；我們以理論計算來輔助證明其轉換機制。
Abstract 1. Se-Ru-CuCl system When [SeRu5(CO)14]2− was treat with different equiv. of CuCl under different conditions, a series of Se-Ru-CO complexes [SeRu5(CO)14CuCl]2−, [SeRu5(CO)14(CuCl)2]2− , [Se2Ru10(CO)28Cu4Cl2]2−, and [Se2Ru4(CO)10Cu2Cl2]2− were isolated. Complexes [Se2Ru10(CO)28Cu4Cl2]2− and [Se2Ru4(CO)10Cu2Cl2]2− were observed in the course of the reaction of [SeRu5(CO)14CuCl]2− with one equivalent of CuCl, proving the transformation relationship between these complexes. DFT calculations were applied to understand experimental results. 2. E-Cr-Mn (E = S, Se ) system In Te-Cr-Mn system, the triangle bipyramidal [PPN]2[Te2CrMn2(CO)9] can transfer into the pyramidal [PPN]2[Te2CrMn2(CO)10] upon the CO addition, but not in E-Cr-Mn (E = S, Se) system. DFT calculations were applied to understand experimental results. Complexe [PPN]2[Te2Cr2Mn2(CO)18], precursor of [PPN]2[Te2CrMn2(CO)9], now can be synthesized in a more simple way. 3. Se-Mn system The reaction of [Se2Mn3(CO)9]− with one equivalent of Cr(CO)6 under 4 M KOH/MeOH solution produced [HSe2CrMn3(CO)14]2− and octahedral [Se2CrMn3(CO)12]3−. Further reation of [HSe2CrMn3(CO)14]2− with Cr(CO)6 in the refluxing CH2Cl2 produced a symmetric complex [HSe2Cr2Mn3(CO)19]2−. [HSe2Cr2Mn3(CO)19]2− can reconvert back to [HSe2CrMn3(CO)14]2− upon the CO addition in THF. DFT calculations were applied to understand the experimental results.
Abstract 1. Se-Ru-CuCl system When [SeRu5(CO)14]2− was treat with different equiv. of CuCl under different conditions, a series of Se-Ru-CO complexes [SeRu5(CO)14CuCl]2−, [SeRu5(CO)14(CuCl)2]2− , [Se2Ru10(CO)28Cu4Cl2]2−, and [Se2Ru4(CO)10Cu2Cl2]2− were isolated. Complexes [Se2Ru10(CO)28Cu4Cl2]2− and [Se2Ru4(CO)10Cu2Cl2]2− were observed in the course of the reaction of [SeRu5(CO)14CuCl]2− with one equivalent of CuCl, proving the transformation relationship between these complexes. DFT calculations were applied to understand experimental results. 2. E-Cr-Mn (E = S, Se ) system In Te-Cr-Mn system, the triangle bipyramidal [PPN]2[Te2CrMn2(CO)9] can transfer into the pyramidal [PPN]2[Te2CrMn2(CO)10] upon the CO addition, but not in E-Cr-Mn (E = S, Se) system. DFT calculations were applied to understand experimental results. Complexe [PPN]2[Te2Cr2Mn2(CO)18], precursor of [PPN]2[Te2CrMn2(CO)9], now can be synthesized in a more simple way. 3. Se-Mn system The reaction of [Se2Mn3(CO)9]− with one equivalent of Cr(CO)6 under 4 M KOH/MeOH solution produced [HSe2CrMn3(CO)14]2− and octahedral [Se2CrMn3(CO)12]3−. Further reation of [HSe2CrMn3(CO)14]2− with Cr(CO)6 in the refluxing CH2Cl2 produced a symmetric complex [HSe2Cr2Mn3(CO)19]2−. [HSe2Cr2Mn3(CO)19]2− can reconvert back to [HSe2CrMn3(CO)14]2− upon the CO addition in THF. DFT calculations were applied to understand the experimental results.
Description
Keywords
(鉻, 錳, 釕)團簇化合物