化合物[Li(THF)4]{W2Cl4[μ-η2-HC(N-2,6-iPr2C6H3)2]2} (1a)與碘化鉀及18-crown-6 ether (冠狀醚)進行陽離子交換可得到化合物
[K(18-c-6)]{W2Cl4[μ-η2-HC(N-2,6-iPr2C6H3)2]2} (2)，將化合物2以KC8進一步還原可得一進行甲基的碳-氫鍵氧化加成反應且有兩個鉀原子橋接在雙鎢(II)間的金屬四重鍵化合物W2H2[μ-K(OEt2)]2[μ-η2-HC(N-
2,6-iPr2C6H3)(N-2-iPr2-6-CH(1-CH2)CH3-C6H3)]2 (3)。將化合物3與四氫呋喃反應可得到同樣進行甲基的碳-氫鍵氧化加成反應且有兩個氫原子橋接在雙鎢(III)間的金屬三重鍵化合物W2(μ-H)2(THF)[μ-η2-HC
(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(1-CH2)CH3-C6H3)]2 (1e)。而用KC8可將化合物1e還原成化合物3，兩者間為可逆的。
化合物1e和3與兩當量的2,4,6-三甲基苯甲腈反應，皆可得到W2(μ-H)2[1-NC(Mes)]2[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(1-CH2)CH3-C6H3)]2 (4)，其苯甲腈以氮原子配位至鎢金屬上。化合物1e和3與兩當量的二苯基鋅反應，皆可得到W2H2[μ-ZnC6H5]2[μ-η2-HC(N-
2,6-iPr2C6H3)(N-2-iPr2-6-CH(1-CH2)CH3-C6H3)]2 (5)，其苯基鋅以架橋形式配位至雙鎢金屬間。化合物3與二乙基氯化鋁反應，可得到
[K(OEt2)4]W2H2(μ-AlEt2)[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(1-
CH2)CH3-C6H3)]2 (6)，其二乙基鋁與鉀進行陽離子置換，以架橋形式配位至雙鎢金屬間。
將WCl4(DME)與兩當量雙氮基脒配基Li[HC(N-2,6-Et2C6H3)2]反應不同時間，可得到順磁性鎢(IV)化合物W[η3-Cl2Li(OEt2)N(2,6-Et2C6
H3)C(H)N(2,6-Et2C6H3)]2 (7)及順磁性鎢(IV)化合物WCl2[η2-HC(N-
2,6-Et2C6H3)2]2 (8)，化合物7脫去兩分子的LiCl，而形成化合物8。將化合物8與一當量的WCl4(DME)反應，可得到順磁性鎢(V)化合物WCl3[η2-HC(N-2,6-Et2C6H3)2]2 (9)。將WCl3(DME)與一當量雙氮基脒配基Li[HC(N-2,6-Et2C6H3)2]2反應，可得到一具有氧原子橋接在雙鎢金屬間的W2Cl2(μ-O)(μ-Cl) [η2-ClLi(OEt2)2Cl][η2-HC(N-2,6-Et2C6H3)2]
[μ-η2-HC(N-2,6-Et2C6H3)2] (10)，將化合物10進一步還原可得到W2(μ-Cl)(μ-CH)(1-N-2,6-Et2C6H3)2[η2-HC(N-2,6-Et2C6H3)2]2 (11)及W4(μ-Cl)4[μ-η2-HC(N-2,6-Et2C6H3)2]4 (12)，化合物11將一分子的雙氮基脒配基進行三原子六電子的切割反應，methylidyne橋接於雙鎢金屬間，兩個imido以terminal的形式配位至鎢金屬上。化合物12為四個鎢(II)金屬以四個氯原子橋接的四重鍵化合物。將化合物10與一當量的雙氮基脒配基Li[HC(N-2,6-Et2C6H3)2]2反應，可得到W2Cl2
(μ-O)(μ-Cl)[η2-HC(N-2,6-Et2C6H3)2]2[μ-η2-HC(N-2,6-Et2C6H3)2] (13)，將化合物13進一步還原可得W2[μ-O(KOEt2)](μ-CH)(1-N-2,6-Et2C6H3)2
[η2-HC(N-2,6-Et2C6H3)2]2 (14)，化合物14與化合物11同樣將雙氮基脒配基進行三原子六電子的切割反應，形成methylidyne的化合物。

The cation exchange between [Li(THF)4]{W2Cl4[μ-η2-HC(N-2,6-iPr2
C6H3)2]2} (1a) and KI in the presence of 18-crown-6 ether affords [K(18-c-6)]{W2Cl4[μ-η2-HC(N-2,6-iPr2C6H3)2]2} (2). Subsequent reduction of 2 gives the quadruply-bonded ditungsten(II) complex W2H2[μ-K(OEt2)]2[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(1-CH2)CH3-C6H3)]2 (3), which is arisen from double intramolecular C-H bond activation and features two potassium counter-cations. Dissolution of 2 in THF affords W2(μ-H)2(THF)[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(1
-CH2)CH3-C6H3)]2 (1e), which displays a gem conformation with two hydrido ligands unsymmetrically bridging two tungsten centers. Complexes 1e and 3 are chemically interconvertible. Reduction of 1e by KC8 gives back to 3.
Treatment of 1e or 3 with 2 equiv of mesityl nitrile yields W2(μ-H)2 [1-NC(Mes)]2[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(1-CH2)CH3
-C6H3)]2 (4), where the nitrogen donor atom of mesityl nitrile coordinates tungsten centers. Reaction of 1e or 3 with 2 equiv of diphenylzinc generates the hetero tetranuclear complex W2H2[μ-ZnC6H5]2[μ-η2-HC(N-
2,6-iPr2C6H3)(N-2-iPr2-6-CH(1-CH2)CH3-C6H3)]2 (5), whereby phenyl zinc bridges two tungsten atoms. Addition of 1 equiv of AlEt2Cl to 3 yields [K(OEt2)4]W2H2(μ-AlEt2)[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH
(1-CH2)CH3-C6H3)]2 (6), whereby diethyl aluminum group bridges two tungsten centers.
Reactions of WCl4(DME) with 2 equiv of lithiated amidinate Li[HC(N-2,6-Et2C6H3)2] in different time periods afford two mononuclear complexes W[η3-Cl2Li(OEt2)N(2,6-Et2C6H3)C(H)N(2,6-
Et2C6H3)]2 (7) and WCl2[η2-HC(N-2,6-Et2C6H3)2]2 (8). Complex 8 can be thought of LiCl extrusion from 7. Upon treatment of 8 with 1 equiv of WCl4(DME), the mononuclear penta-valent tungsten complex WCl3[η2-
HC(N-2,6-Et2C6H3)2]2 (9) is obtained.
On the other hand, the reaction of WCl3(DME) with 1 equiv of Li[HC(N-2,6-Et2C6H3)2] affords the dinuclear “-ate” complex W2Cl2
(μ-O)(μ-Cl)[η2-ClLi(OEt2)2Cl][η2-HC(N-2,6-Et2C6H3)2] [μ-η2-HC(N-
2,6-Et2C6H3)2] (10), which features an oxygen atom bridging two tungsten centers. Subsequent reduction of 10 gives the methylidyne complex W2(μ-Cl)(μ-CH)(1-N-2,6-Et2C6H3)2[η2-HC(N-2,6-Et2C6H3)2]2
(11) and the tetranuclear complex W4(μ-Cl)4[μ-η2-HC(N-2,6-Et2C6H3)2]4 (12). Complex 11 is formed through a three-atom 6e reductive cleavage of the amidinate to give a bis-terminal imido and bridging methylidyne ditungsten complex. Complex 12 is the quadruply-bonded complex, which has four tungsten(II) centers with four chloride atoms bridging to the tungsten centers. Further reaction of 10 with 1 equiv of Li[HC(N-2,6-Et2C6H3)2] affords W2Cl2(μ-O)(μ-Cl)[η2-HC(N-2,6-Et2C6
H3)2]2[μ-η2-HC(N-2,6-Et2C6H3)2] (13). Subsequent reduction of 13 also induces the cleavage of the amidinato ligand to give the methylidyne complex W2[μ-O(KOEt2)](μ-CH)(1-N-2,6-Et2C6H3)2[η2-HC(N-2,6-Et2
C6H3)2]2 (14).

中文摘要................I
Abstract..............III
謝誌....................V
目錄....................VII
圖目錄...................X
方程式目錄...............XII
第一章 緒論...............1
1-1. 金屬-金屬多重鍵的發展............1
1-2. 金屬-金屬多重鍵錯合物的反應性.....8
1-3. 金屬-金屬五重鍵錯合物的反應性.....10
1-4. 研究目的.......................12
第二章 追求雙鎢金屬五重鍵錯合物.........13
2-1. 前言...........................13
2-2. 錯合物2及3之合成與討論 ...........15
2-3. 結論...........................19
第三章 雙鎢金屬多重鍵錯合物之反應性探討...21
3-1. 前言(腈類反應性之探討)............21
3-2. 錯合物4之合成與探討...............23
3-3. 前言(有機鋅化合物反應性之探討)......27
3-4. 錯合物5之合成與探討................28
3-5. 前言(有機鋁化合物反應性之探討).......33
3-6. 錯合物6之合成與探討................34
第四章 合成具有次甲基橋接之雙鎢金屬化合物....38
4-1. 前言................38
4-2. 錯合物7及8的合成與探討 ............38
4-3. 錯合物9的合成與探討...............42
4-4. 錯合物10的合成與探討..............44
4-5. 錯合物11及12之合成與探討...........47
4-6. 錯合物13之合成與探討..............52
4-7. 錯合物14的合成與探討..............54
4-8. 錯合物11及14比較與討論............56
4-9. 結論............................57
第五章 其他嘗試.......................59
5-1. 與氣體的反應(NO、CO、CO2)........59
5-2. 與疊氮化物的反應(NaN3、TMSN3)....61
5-3. 與腈類化合物的反應(CH3CN、PhCN 、TMSCN)..........62
5-4. 與烯類化合物的反應(3-Hexyne、phenylacetylene、1-pentyne)..........................................64
5-5. 與ZnR2及AlR3化合物的反應(AlPh3、AlMe3、ZnMe2、ZnEt2)............................................66
5-6. 與金屬鹵化物化合物的反應(YbI2(THF)2、CrCl2)......68
5-7. 與Pd(PPh3)4 、BEt3、AgOTf的反應................70
第六章　實驗步驟與晶體結構資料.........................72
6-1. 一般操作......................................72
6-2. 實驗使用儀器...................................72
6-3. 實驗溶劑與藥品.................................73
6-4. 實驗步驟......................................74
6-4-1. [K(18-c-6)]{W2Cl4[μ-η2-HC(N-2,6-iPr2C6H3)2]2} (2)錯合物的合成...........................................74
6-4-2. W2H2[μ-K(OEt2)]2[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(1- CH2)CH3-C6H3)]2 (3)錯合物的合成.............75
6-4-3. W2(μ-H)2[1-NC(Mes)]2[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6- CH(1-CH2)CH3-C6H3)]2 (4)錯合物的合成......76
6-4-4. W2H2(μ-ZnC6H5)2[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(1- CH2)CH3-C6H3)]2 (5)錯合物的合成.............78
6-4-5. [K(OEt2)4]W2H2(μ-AlEt2)[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6- CH(1-CH2)CH3-C6H3)]2 (6)錯合物的合成.......79
6-4-6. W[η3-Cl2Li(OEt2)N(2,6-Et2C6H3)C(H)N(2,6-Et2C6H3)]2 (7)錯合物的合成......................................81
6-4-7. WCl2[η2-HC(N-2,6-Et2C6H3)2]2 (8)錯合物的合成........81
6-4-8. WCl3[η2-HC(N-2,6-Et2C6H3)2]2 (9)錯合物的合成........82
6-4-9. W2Cl2(μ-O)(μ-Cl)[μ-η2-HC(N-2,6-Et2C6H3)2][η2-HC(N-2,6- Et2C6H3)2][η2-ClLi(OEt2)2Cl] (10)錯合物的合成......82
6-4-10. W2(μ-Cl)(μ-CH)(1-N-2,6-Et2C6H3)2[η2-HC(N-2,6-Et2
C6H3)2]2 (11)錯合物的合成..................................84
6.4.11. W4(μ-Cl)4[μ-η2-HC(N-2,6-Et2C6H3)2]4 (12)錯合物的合成.......................................................86
6-4-12. W2Cl2(μ-O)(μ-Cl)[η2-HC(N-2,6-Et2C6H3)2]2[μ-η2-HC(N-2,6- Et2C6H3)2] (13)錯合物的合成........................87
6-4-13. W2[μ-O(KOEt2)](μ-CH)(1-N-2,6-Et2C6H3)2[η2-HC(N-2,6- Et2C6H3)2]2 (14)錯合物的合成.......................89
6-5. 晶體結構資料..........................................91
6-5-1. W2H2[μ-K(OEt2)]2[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(1- CH2)CH3-C6H3)]2 (3)的晶體結構資料..................91
6-5-2. W2(μ-H)2[1-NC(Mes)]2[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6- CH(1-CH2)CH3-C6H3)]2 (4)的晶體結構資料...........92
6-5-3. W2H2(μ-ZnC6H5)2[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6-CH(1- CH2)CH3-C6H3)]2 (5)的晶體結構資料..................93
6-5-4. [K(OEt2)4]W2H2(μ-AlEt2)[μ-η2-HC(N-2,6-iPr2C6H3)(N-2-iPr2-6- CH(1-CH2)CH3-C6H3)]2 (6)的晶體結構資料...........94
6-5-5. W[η3-Cl2Li(OEt2)N(2,6-Et2C6H3)C(H)N(2,6-Et2C6H3)]2 (7)的晶體結構資料..........................................95
6-5-6. WCl2[η2-HC(N-2,6-Et2C6H3)2]2 (8)的晶體結構資料......96
6-5-7. WCl3[η2-HC(N-2,6-Et2C6H3)2]2 (9)的晶體結構資料......97
6-5-8. W2Cl2(μ-O)(μ-Cl)[μ-η2-HC(N-2,6-Et2C6H3)2][η2-HC(N-2,6- Et2C6H3)2][η2-ClLi(OEt2)2Cl] (10)的晶體結構資料....98
6-5-9. W2(μ-Cl)(μ-CH)(1-N-2,6-Et2C6H3)2[η2-HC(N-2,6-Et2C6H3)2]2 (11)的晶體結構資料.............................99
6-5-10. W4(μ-Cl)4[μ-η2-HC(N-2,6-Et2C6H3)2]4 (12)的晶體結構資料.......................................................100
6-5-11. W2Cl2(μ-O)(μ-Cl)[η2-HC(N-2,6-Et2C6H3)2]2[μ-η2-HC(N-2,6- Et2C6H3)2] (13)的晶體結構資料......................101
6-5-12. W2[μ-O(KOEt2)](μ-CH)(1-N-2,6-Et2C6H3)2[η2-HC(N-2,6- Et2C6H3)2]2 (14)的晶體結構資料.....................102
第七章 參考文獻............................................103

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