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

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

陳漢宮(Chen, Han Gung)

指導教授 ： 蔡易州

國立清華大學/理學院/化學系/碩士(2013年)

https://doi.org/10.6843/NTHU.2013.00400

摘要

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。

關鍵字

雙鉬五重鍵

並列摘要

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.

參考文獻

23. 顏君旭, 國立清華大學化學研究所碩士論文. 2009.

8. Tsai, Y.-C.; Wang, P.-Y.; Chen, S.-A.; Chen, J.-M. J. Am. Chem. Soc. 2007, 129, 8066.

9. Tsai, Y.-C.; Wang, P.-Y.; Chen, S.-A.; Chen, J.-M. J. Am. Chem. Soc. 2007, 129, 8066.

22. Hsu, C. W.; Yu, J.S.; Yen, C. H.; Lee, G. H.; Wang. Y.; Tsai, Y. C. Angew. Chem. In.t Ed. 2008, 47, 9933.

25. Chen, H. Z.; Liu, S. C.; Yen, C. H.; Yu, J. S. K.; Shieh, Y. J.; Kou, T. S.; Tsai, Y. C. Angew. Chem. Int. Ed. 2012, 51, 10342.