Title

雙鉬金屬五重鍵與苯醯基鹵化物、烷醯基鹵化物及含氮雜苯反應研究

Translated Titles

Reactivity of the Mo-Mo Quintuple Bond with Benzoyl Halide、 Alkyl Halide and Aza-Containing Arene

DOI

10.6843/NTHU.2013.00400

Authors

陳漢宮

Key Words

雙鉬五重鍵

PublicationName

清華大學化學系所學位論文

Volume or Term/Year and Month of Publication

2013年

Academic Degree Category

碩士

Advisor

蔡易州

Content Language

繁體中文

Chinese Abstract

本論文以高立體阻礙的雙氮基脒配基合成出的雙鉬金屬五重鍵Mo2[μ-2-N-HC(2,6-i-Pr2C6H3)2]2 (1),用其低配位與低價數的性質與小分子進行反應。錯合物1與兩當量苯甲醯基鹵化物反應,得到Mo2(X)(μ-X)(μ-C-Ar)(κ2-O2C-Ar)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (2) X = Cl、 Ar = Ph; (3) X = Cl、 Ar = 4-FC6H4; (4) X = Cl、 Ar = 2-MeC6H4; (5) X = Br、 Ar = Ph; (6) X = F、 Ar = Ph,活化了苯甲醯基鹵化物的碳-氧鍵,形成次苄基配位基與鹵素橋接在鉬-鉬雙鍵中,且苯甲酸基與另一個鹵素各自配位在其中一個鉬上;其中兩量當量的苯甲基氟反應有另一產物Mo2(-2-1,2:2-4,5-PhCOF)[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2 (7)為一燈籠型結構錯合物。 此外,錯合物1與一當量的苯甲醯基鹵化物可得Mo2(Cl)(μ-2-OC-4-FC6H4)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (8) X = Cl、 Ar = 4-FC6H4; (9) X = Cl、 Ar = 2-MeC6H4; (10) X = Br、 Ar = Ph; (11) X = Cl、 Ar = Ph,苯甲醯基鹵化物進行氧化加成以反式(trans)方式配位在雙鉬原子上。 將錯合物11與2-甲基苯甲醯氯反應,可得Mo2(Cl)(μ-Cl)(μ-CPh)(κ2-O2C-2-MeC6H4)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (12);錯合物9與苯甲醯氯反應,可得Mo2(Cl)(μ-Cl)(μ-C-2-MeC6H4)(κ2-O2Ph)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (13),第二當量的苯甲醯基氯化物會形成苯甲酸基的配基。將錯合物10與苯甲醯氯反應,可得Mo2(X)(μ-X)(μ-CPh)(κ2-O2CPh)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 2、 5、 (14)、 (15) (X = 50% Cl + 50% Br)。 將錯合物1與一當量的三甲基乙醯氯反應,為Mo2(Cl)(μ-2-OC-C(CH3)3)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (16),三甲基乙醯氯氧化加成以反式(trans)方式配位在雙鉬原子上;錯合物1與一當量的苯甲醯氯反應,為Mo2(Cl)(μ-Cl)(μ-CPh)(κ2-O2C(CH3)3)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (17) ,第二當量的苯甲醯氯會形成苯甲酸基配位在一個鉬原子上,錯合物1與兩當量的乙醯氯反應,為Mo2(Cl)(μ-Cl)(μ-C-Me)(κ2-O2CMe)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (18) ,形成次乙基與氯離子橋接在鉬-鉬雙鍵中,且乙酸基與另一個氯離子各自配位在其中一個鉬上;錯合物3加入三當量鉀石磨(KC8),得到Mo2(μ-C-4-FC6H4)(κ1-O2C-4-FC6H4)[μ-2-N-HC(2,6-i-Pr2C6H3)2]2 (19) ,為兩個氯被還原的產物。 另外,錯合物1與兩當量苯甲醛反應,得Mo2[μ-κ2-(OCHPh)2][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (20),苯甲醛進行碳-碳鍵耦合形成配基,以兩個氧原子配位在鉬原子上;錯合物1與四當量苯甲醛反應,得Mo2[μ-κ2-(OCHPh)2]2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (21),苯甲醛進行碳-碳鍵耦合形成配基,呈現風車型結構;錯合物20與兩當量苯甲腈反應,得Mo2(NCPh)2[μ-κ2-(OCHPh)2][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (22),苯甲腈以氮原子配位在鉬原子上。 錯合物1與鄰二氮雜苯反應,產生Mo2(2-2-1,2-C4H4N2)2[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2 (23),兩分子的鄰二氮雜苯由氮原子配位在鉬原子上;錯合物1與對二氮雜苯反應,形成Mo2(-2-1,2:2-4,5-C4H4N2)[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2 (24),為一燈籠型結構;錯合物1與3,6-二苯基-1,2,4,5-四嗪反應,得Mo2(-2-1,5:2-2,4-C14H10N4)[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2 (25) ,為一燈籠型結構。

English Abstract

The low-coordinate quintuple bonded dimolybdenum complex Mo2[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2 (1) displays remarkable reactivity with organic compound. Treatment of 1 with two equiv of benzoyl halide, affords a novel dimolybdenum complex , Mo2(X)(μ-X)(μ-C-Ar)(κ2-O2C-Ar)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (2) X = Cl、 Ar = Ph; (3) X = Cl、 Ar = 4-FC6H4; (4) X = Cl、 Ar = 2-MeC6H4; (5) X = Br、 Ar = Ph; (6) X = F、 Ar = Ph. Complex 2-6 contains one benzylidyne between two molybdenum centers. Among, reaction of 1 with two equiv of benzoyl fluoride, gives another complex, Mo2(-2-1,2:2-4,5-PhCOF)[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2 (7). Treatment of 1 with one equiv of benzoyl halide leads to formation of Mo2(X)(μ-2-Ar)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (8) X = Cl、 Ar = 4-FC6H4; (9) X = Cl、 Ar = 2-MeC6H4; (10) X = Br、 Ar = Ph; (11) X = Cl、 Ar = Ph, which are formed via an oxidative addition of one molecular benzoyl halide to 1. Treatment of 11 with one equiv of 2-methylbenzoyl chloride, affords dimolybdenum complex, Mo2(Cl)(μ-Cl)(μ-CPh)(κ2-O2C-2-MeC6H4)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (12). On the other hand, treatment of 11 with one equiv of benzoyl chloride, affords dimolybdenum complex , Mo2(Cl)(μ-Cl)(μ-C-2-MeC6H4)(κ2-O2Ph)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (13). The reaction of 5 with one equiv of benzoyl chloride gives Mo2(X)(μ-X)(μ-CPh)(κ2-O2CPh)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 2、 5、 (14)、 (15) (X = 50% Cl + 50% Br). Treatment of 1 with one equiv of trimethylacetyl chloride, affords Mo2(Cl)(μ-2-OC-C(CH3)3)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (16). Then the reaction of 16 with one equiv of benzoyl chloride gives Mo2(Cl)(μ-Cl)(μ-CPh)(κ2-O2C(CH3)3)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (17). Beside, treatment of 1 with two equiv of acetyl chloride, affords Mo2(Cl)(μ-Cl)(μ-C-Me)(κ2-O2CMe)[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (18). Addition of three equiv KC8 to complex 3 affords Mo2(μ-C-4-FC6H4)(κ1-O2C-4-FC6H4)[μ-2-N-HC(2,6-i-Pr2C6H3)2]2 (19), which is formed via reductive elimination. The reaction of 1 with two equiv of benzaldehyde gives Mo2[μ-2-(OCHPh)2][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (20), which result from C-C coupling of two benzaldehyde. Furthermore, the reaction of 1 with four equiv of benzaldehyde affords Mo2[μ-2-(OCHPh)2]2[μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (21). Treatment of 20 with two equiv of benzonitrile, affords Mo2(NCPh)2[μ-2-(OCHPh)2][μ-κ2-HC(N-2,6-iPr2C6H3)2]2 (22) Treatment of 1 with equimolar amount of pyridazine, 3,6-diphenyl-1,2,4,5-tetrazine, or pyrazine gives the quadruple bonded dinuclear compounds Mo2(2-2-1,2-C4H4N2)2[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2 (23), Mo2(-2-1,2:2-4,5-C4H4N2)[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2 (24), and Mo2(-2-1,6:2-2,5-C14H10N4)[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2 (25), respectively. It is interesting to note that 23 has two 2-ligated pyridazine molecules displaying a paddlewheel configuration, while 24, and 25 display 4-bound arene ligands.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學系所
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