REACTIONS OF THE TRINUCLEAR [2.2]PARACYCLOPHANE CLUSTER RU-3(CO)(9)(MU(3)-ETA(2)ETA(2)ETA(2)-C16H16) - THERMAL-ACTIVATION VERSUS CHEMICAL ACTIVATION

The reactivity of the known [2.2]paracyclophane triangular cluster RU(3)(CO)(9)(mu(3).eta(2):eta(2):eta(2). C16H16) (1) has been studied. Thermolysis of(1) with Ru-3(CO)(12) in octane yields the known octahedral carbido complex RU(6)C(CO)(14)(mu(3)-eta(2):eta(2):eta(2)-C16H16) (2). Reaction of 1 with Me(3)NO in dichloromethane results in cluster degradation and formation of the bridged dimer RU(2)-(CO)(6)(mu(2)-eta(3):eta(3)-C16H16) (3) Likewise, treatment of 2 with Me(3)NO in dichloromethane results in cluster degradation and affords 1. Mild thermolytic action of 1 with the alkyne C(2)Ph(2) affords three products: RU(3)(CO)(7)(mu(3)-eta(1):eta(2):eta(1)-C(2)Ph(2))(eta(6)-C16H16) (4), in which the cyclophane now adopts a terminally banding mode, Ru-3(CO)(7)(mu(3)-eta(2)-PhC(2){PhCO})(eta(6)-C16H16) (5), similar to 4 except that carbonyl insertion has occurred between the alkyne and metal; and the dinuclear product Ru-2(CO)(6)({mu(2)-sigma:eta(2)-C(2)Ph(2)}(2)-CO) (6), in which a carbonyl has been inserted between two alkynes. 4 is also produced when 1 is treated with Me(3)NO in the presence of C(2)Ph(2). 1 undergoes reaction either with Me(3)NO in the presence of PPh(3) or by direct thermolysis with PPh(3) to yield the monosubstituted derivative RU(3)(CO)(8)(PPh(3))(mu(3)-eta(2):eta(2):eta(2)- C16H16) (7) AU compounds 3, 4, 6, and 7 have been characterized by both spectroscopic means and single crystal X-ray diffraction methods. 5 has been characterized by spectroscopy only, and the C-13 NMR spectrum of cluster 1 is also reported.