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.