107820-83-7Relevant articles and documents
N-N double bond cleavage and the ortho metalation of azoarenes using Ru3(NPh)(CO)10
Smieja, Joanne A.,Gozum, John E.,Gladfelter, Wayne L.
, p. 1311 - 1317 (2008/10/08)
The reaction of Ru3(NAr)(CO)10 with azoarenes under CO results in the cleavage of the N-N double bond to yield Ru3(NAr)2(CO)9 and ArNCO. In the absence of CO the insertion into one of the C-H bonds ortho to the azo functional group also occurs. The product distribution is sensitive to the para substituent on the azobenzene, with electron-withdrawing groups favoring N=N bond cleavage, while ortho metalation is favored with electron-donating groups. A single-crystal X-ray crystallographic study of one of the clusters containing an ortho-metalated azoarene, HRu3(NPh)(CH3OC6H3NNC 6H4OCH3)(CO)8 [P1 space group, a = 9.237 (4) ?, b = 10.917 (6) ?, c = 17.199 (6) ?, α = 100.47 (3)°, β = 99.80 (3)°, γ = 90.59 (4)°, Z = 2], revealed a closed trinuclear cluster containing a triply bridging NPh, a semibridging carbonyl, an ortho-metalated azoarene, and a bridging hydride trans to the carbon of the ortho-metalated ring. Spectroscopic methods indicate the cluster interconverts in solution at room temperature among three isomers. Reaction of HRu3(NPh)(CH3OC6H3NNC 6H4OCH3)(CO)8 with carbon monoxide leads to N-N double bond cleavage, while the reaction with excess azoarene yields a new cluster containing two ortho-metalated azoarenes. The analogous reaction of Ru3(NPh)(CO)10 with N-phenylbenzaldimine was also examined and found to give only the product resulting from ortho metalation of the phenyl ring.
