Cluster chemistry: LIII. Preparation and some substitution reactions of bis(arylimido)triruthenium complexes: X-ray structures of Ru3(μ 3-NPh) (μ3-NC6 H4 F-3) (CO)9 and Ru3(μ3-NPh)2(CO)8(L) (L = CNC6H3Me2-2,6 and PPh3)

摘要: Abstract Azoarenes, ArNNAr′, react with Ru3(CO)12 to give Ru3(μ3-NAr)(μ3- NAr′)(CO)9 (Ar = Ph, Ar′ C6H4Me-3, C6H4CF3-3, C6H4F-3 (11), C6H4F-4; Ar Ar′= C6H4Me-3) in moderate yields; for Ph or the mononuclear cyclometallated Ru(C6H3RNNC6H4R-3)2(CO)2 (R H Me) were also obtained low yield. Fe3(CO)12 and azobenzene afford Fe3(μ3-NPh)2(CO)9 very An X-ray study of 11 confirms structural assignments made on basis spectroscopic measurements: an Ru3 triangle a non-bonded Ru…Ru vector is capped both sides by μ3-arylimido moiety. Electron transfer-catalysed reactions isocyanides, tertiary phosphines phosphites proceed CO-substituted products yields: complexes Ru3(μ3- NPh)2(CO)8(L) (L CNC6H3Me2-2,6 (15), PPh3 (16), P(OMe)3), {Ru3(μ3- NPh)2(CO)8}2(μ-(PPh2)2C2) Ru3(μ3-NPh)2(μ-LL)(CO)7 (LL dppm, dppe) obtained. studies 15 16 show that isocyanide ligand occupies axial position, whereas phosphine takes up equatorial terminal ruthenium atom. Crystals 11, crystallize monoclinic system space group P21/n, 11.496(2), b 14.020(2), c 15.735(2) A, β 99.43(1)°, Z=4 11; 11.933(2), 18.952(2), 14.370(4) 100.29(2)°, 15; Pc, 17.507(3), 11.657(2), 19.518(4) 100.41(2)°, Z 4 16. The structures refined least-squares methods at convergence R 0.037, Rw= 0.048 3653 statistically significant reflections 0.041, Rw 0.046 3903 0.039, 0.047 5291