1. 合成具不對稱雙氮基脒配位基之雙鉻五重鍵錯合物 2. 1,2-苯基及1,2-吡嗪雙鉬四重鍵錯合物之氧化反應

王韻涵

doi:10.6843/NTHU.2012.00235

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1. 合成具不對稱雙氮基脒配位基之雙鉻五重鍵錯合物 2. 1,2-苯基及1,2-吡嗪雙鉬四重鍵錯合物之氧化反應

1. Synthesis of Quintuple Bonded Dichromium Complexes with Unsymmetrical Amidinates 2. Oxygenation of Quadruply-Bonded 1,2-Dimolybdenumbenzene and -pyrazine

王韻涵 , Masters　　Advisor：蔡易州　　

繁體中文 DOI： 10.6843/NTHU.2012.00235

雙鉻五重鍵；不對稱雙氮基脒配位基；雙鉬四重鍵；氧化反應

Abstract │ Reference (93) │ Altmetrics

Abstract 〈TOP〉

本論文第一部份主要研究目標為合成具有不對稱雙氮基脒配基
的雙鉻五重鍵錯合物。選擇甲基作為不對稱雙氮基脒配基上取代基，
2,6-雙異丙基及2,6-雙甲基作為苯環上取代基並加入1.1 當量的氯化
鉻(II)，可得到文獻上少見的扭曲雙三角錐(distorted bipyramidal)結構的雙核鉻二價金屬錯合物(μ-Cl)2[Cr(THF)]2[(2,6-iPr2C6H3)NC(H3C)
N(2,6-Me2C6H3)]2 (1)，將其加入2.1 當量KC8，可成功還原得到配基
橋接(bridge) 於雙鉻金屬上的不對稱雙鉻五重鍵錯合物
Cr2[(2,6-iPr2C6H3)NC(H3C)N(2,6-Me2C6H3)]2 (2) ， 其鉻- 鉻鍵長為1.7370(17) Å 。將2,6-雙甲基置換為3,5-雙甲基、4-甲基以及2,6-雙
氟基所合成的不對稱雙氮基脒配基加入1.1 當量的氯化鉻(II)，同樣可
得到具扭曲雙三角錐結構的雙核鉻二價金屬錯合物
(μ-Cl)2[Cr(THF)]2[(2,6-iPr2C6H3)NC(H3C)N(R)]2 (R = 3,5-Me2C6H3, (3)；R = 4-MeC6H3；R = 2,6-F2C6H3, (6))。加入2.1 當量KC8 還原之則僅得到兩片配基以螯合(chelate)方式鍵結於鉻金屬上的單核鉻金屬錯合物Cr[(2,6-iPr2C6H3)NC(H3C)N(R)]2 (R = 3,5-Me2C6H3, (4)；R = 4-MeC6H3,(5)：R = 2,6-F2C6H3, (7))。
本論文第二部份主要研究目標為1,2-苯基及1,2-吡嗪雙鉬四重
鍵錯合物的氧化加成反應。將正戊炔、三甲基矽乙炔或苯甲腈加入雙
鉬五重鍵錯合物Mo2[μ-η2-(Ph)C(N-2,6-iPr2C6H3)2]2，會在雙鉬金屬上
進行[2+2+2]環化加成反應，產生具有燈籠型(lantern-type)結構的1,2-
苯基及1,2-吡嗪雙鉬四重鍵錯合物。將氧氣通入此些雙鉬四重鍵錯合
物可分別得到： (μ-η2:η2-1,3-nPr2-2-butenyl)(MoO)2[η2-(Ph)C(N-2,6-iPr2C6H3)2]2 (8)，雙鉬鍵長為2.7470(6) Å ，為一分子氧氣以末端
(terminal)形式分別接在兩個鉬原子上，原有的六員環翻轉約九十度而
垂直於鉬- 鉬鍵的雙鉬單鍵錯合物； (μ-O)(μ-CCHC(SiMe3)CHO)
(η1-OSiMe3)(MoO)[η2-(Ph)C(N-2,6-iPr2C6H3)2]2 (9)包含兩分子的氧氣，其中兩個氧原子分別以末端和橋接形式接於鉬金屬上，而另一分子氧
氣則個別嵌入(insert)芳香環中之碳原子及三甲基矽乙炔上，雙鉬鍵長
為2.6284(3) Å，屬於鉬鉬單鍵錯合物。(μ-O)2(μ-η1:η1-NC(Ph)C(Ph)N)Mo2[η2-(Ph)C(N-2,6-iPr2C6H3)2]2 (10)之芳香六員環仍存在，鉬-鉬鍵鍵長為2.4859(3) Å ，一分子氧氣直接以μ-⊥的方式在鉬-鉬鍵上進行
1,2-氧化加成反應，橋接於兩個鉬金屬上形成雙鉬雙重鍵錯合物。此
外，將吡啶-氮-氧化物與1,2-吡嗪雙鉬四重鍵錯合物進行氧化加成反
應，可得到與10 結構相近同具芳香性六員環之雙鉬三重鍵錯合物
(μ-O)(μ-η1:η1-NC(Ph)C(Ph)N)Mo2[μ-η2-(Ph)C(N-2,6-iPr2C6H3)2]2 (11)，其鉬-鉬鍵鍵長為2.3317(7) Å ，僅具一個橋接至鉬金屬上的氧原子，並被配基包圍住，使第二個氧原子無法繼續進入。

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