SYNTHESIS OF 1,3-DIARYLTRIAZENIDO TRIRUTHENIUM AND TRIOSMIUM CLUSTERS- CRYSTAL-STRUCTURES OF [RU-3(MU-H)(CO)(10)(MU-C6F5NNNC6F5)] AND [OS-3(CO)(11)CL(ETA(2)-C6F5NNNC6F5)]
Hg. Ang et al., SYNTHESIS OF 1,3-DIARYLTRIAZENIDO TRIRUTHENIUM AND TRIOSMIUM CLUSTERS- CRYSTAL-STRUCTURES OF [RU-3(MU-H)(CO)(10)(MU-C6F5NNNC6F5)] AND [OS-3(CO)(11)CL(ETA(2)-C6F5NNNC6F5)], Journal of the Chemical Society. Dalton transactions, (8), 1996, pp. 1573-1581
New clusters [Ru-3(mu-H)(CO)(10)(mu-RNNNR)](R = p-C(6)F(4)X; X = F 1,
Pr 2, I 3 or H 4) were obtained from reactions of RN=NNHR with [Ru-3(C
O)(12)] in toluene at 80 degrees C under vacuum, while the linear trio
smium clusters [Os-3(CO)(11)Cl(eta(2)-RNNNR)] (R = p-C(6)F(4)X; X = F
5, Br 6, I 7 or H 8) were obtained from RN=NNHR with [Os-3(CO)(11)(NCM
e)] in CH2Cl2 at 60 degrees C under vacuum. The crystal structures of
[Ru-3(mu-H)(CO)(10)(mu-C6F5NNNC6F5)] 1 and [Os-3(CO)(11)Cl(eta(2) -C6F
5NNNC6F5)] 5 have been determined by single-crystal X-ray crystallogra
phy. The structure of 1 shows that the triazenide ligand bridges one R
u-Ru vector in the cluster at axial sites and forms a five-membered ri
ng with pi delocalization over the whole system. A hydride ligand was
located which bridges another Ru-Ru vector equatorially and displays i
nteresting fluxionality in solution. The chloride ligand in complex 5
co-ordinates equatorially at the first Os atom, while the triazenide o
ccupies an axial and an equatorial site on the third Os in the linear
cluster and forms a four-membered ring with pi delocalization over the
whole system. The linear cluster [Os3H(CO)(11)(eta(2)-C6F5NNNC6F5)],
precursor of 5, was also obtained. Carbon-13 NMR studies of this clust
er and the mechanism of its formation are reported.