33310-08-6Relevant academic research and scientific papers
Binuclear metallapyrrolidone complexes formed from coupling of CO and alkynes with the μ3-nitrene ligand of Ru3(μ3-NPh)(CO)10
Han, Sung-Hwan,Geoffroy, Gregory L.,Rheingold, Arnold L.
, p. 2380 - 2386 (2008/10/08)
The μ3-nitrene cluster Ru3(CO)10(μ3-NPh) (1) reacts with PhC≡CPh and MeC≡CPh to give the binuclear metallapyrrolidone complexes Ru2(CO)6(μ2-η3-PhC=CRC(O)NPh) (2, R = Ph; 5, R = Me) which form by combination of the alkyne with CO and the nitrene ligand. Minor products from the reactions are metallacyclopentadiene complexes, Ru2(C4R2Ph2)(CO)6, Ru4(CO)11(μ4-NPh)(MeC≡CPh), and the unusual Ru5 cluster Ru2(μ2-η3-PhC=CPhC(O)NPh)(CO) 5·Ru3(μ3-NPh)(CO) 6(μ3-CO) (3). The structures of 2, 3, and 5 have been crystallographically established. 2: monoclinic, P21/c, a = 21.492 (5) A?, b = 7.840 (1) A?, c = 15.819 (4) A?, β = 100.6 (2)°, V = 2619.4 (9) A?3, Z = 4, R = 0.030, Rw = 0.035 from 4417 reflections with Fo ≥ 3σ(Fo). 3: monoclinic, P21/c, a = 15.315 (5) A?, b = 27.319 (10) A?, c = 20.593 (7) A?, β = 102.46 (3)°, V = 8412 (7) A?3, Z = 4, R = 0.059, Rw = 0.058 for the 5783 reflections with Fo ≥ 3σ(Fo). 5: monoclinic, P21/c, a = 7.732 (1) A?, b = 30.670 (7) A?, c = 19.432 (4) A?, β = 99.96°, V = 4538 (2) A?3, Z = 4, R = 0.035, Rw = 0.038 for 5061 reflections with Fo ≥ 4σ(Fo). Complexes 2 and 5 have a μ2-η3-PhC=C(R)-C(O)-NPh ligand bridging between the Ru atoms which are joined by a metal-metal bond. Each Ru is further ligated by three CO's. Compound 3 derives from combination of 1 with 2. It has the μ3-CO ligand of 1 bound to one Ru atom of 2 in an isocarbonyl fashion and one Ph ring of the μ2-η3-PhC=C(Ph)-C(O)-NPh ligand having replaced three CO's on a single Ru atom of 1. Complex 3 was also directly prepared from the combination of 1 with 2 in refluxing cyclohexane. The diruthenium complex 2 further reacts with PhC≡CPh to form pentaphenylpyridinone and Ru3(PhC≡CPh)2(CO)8 (10). Complex 2 also reacts with CO upon photolysis to form 1,3,4-triphenylmaleimide.
