Ruthenium-triazene complexes as latent catalysts for UV-induced ROMP
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European Journal of Inorganic Chemistry 2013 (31): 5462--5468 (2013)

Three novel ruthenium(II) complexes, Grubbs' catalyst analogs, bearing triazene group, RuX2(IMesH2)N,N-diethyl-N'-(2-benzylidene)triazene (IMesH2 = 1,3-dimesitylimidazolin-2-ylidene; 2-4; X = Cl, CF3CO2, C6F5CO2) are prepd. and tested as photo-induced ring-opening metathetic polymn. of cycloalkenes. Single-crystal x-ray structure anal. of compds. 2-4 revealed that the triazene ligand exists in the trans form and that the aryl-connected nitrogen atom of the triazene binds to the ruthenium atom to form a five-membered chelate ring. Compds. 2-4 were applied to the UV-induced ring-opening metathesis polymn. (ROMP) of cis-cyclooctene (5) and dicyclopentadiene (6). Whereas all three precatalysts show pronounced thermal latency in the presence of 5 or 6, only compd. 2 displays significant photo-ROMP activity. The photoreactivity of precatalysts 2-4, which decreases with increasing electron-withdrawing character and with decreasing pKa of the X groups, is discussed and correlated with the x-ray data of 2-4, with low-temp. 1H NMR measurements as well as with cyclovoltammetric measurements. on SciFinder(R)
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