Photosubstitution of (Fulvalene)tetracarbonyldiruthenium by Alkenes and Alkynes:  First Observation of Alkyne Coupling on Fulvalene Dimetals and Synthesis of a (Fulvalene)dimetallacyclopentadiene(alkene) Complex

Abstract

Irradiation (λ max = 300-375 nm) of FvRu 2 (CO) 4 (1, Fv = η 5 :η 5

Intramolecular Double C-H Activation in FvM2(en)4(Fv=fulvalene; M=Ir, Rh; en=ethylene)

“…However, it seems rather unclear that this photochemical reaction does not afford any benzene coordination after loss of ethylene in contrast to previous Here we notice that the sp 2 C-H bond of coordinated ethylene here is already weaker than the free phenyl C-H bond; therefore, intramolecular C-H bond activation takes place to yield the doubly activated product (23).…”

“…During this photoreaction the hydrido ethyl intermediate formation can be evidenced by previous reaction 13, 14, 18. However, the photochemical reaction of 13 in benzene under the similar reaction condition to the previous one gave a rather unexpected product (23), which may be in part explained by loss of one ethylene on photolysis, followed by the corresponding vinyl hydrido complex (22), eventually leading to the doubly C-H activated product (23) 19 with loss of H 2 14 (Scheme 8). However, it seems rather unclear that this photochemical reaction does not afford any benzene coordination after loss of ethylene in contrast to previous Here we notice that the sp 2 C-H bond of coordinated ethylene here is already weaker than the free phenyl C-H bond; therefore, intramolecular C-H bond activation takes place to yield the doubly activated product (23).…”

“…This photochemical reaction was performed in 1.5 mM solution of the reactant in degassed dry benzene by a broad-band Hanovia 450 W medium Hg-vapor lamp with a water-cooled jacket (Scheme 4). 14,21,22,23 In this report, we reveal the first sytheses of FvIr 2 (en) 4 (12) 15 and FvRh(en) 4 valene was then introduced into the reaction solution at 0 o C with ethylene bubbling for more than 1hr, leading to a deep orange precipitation. This product solution was passed through Celite column and solvent was removed under vacuum.…”

Synthesis, structures and reactions of doubly bridged biscyclopentadienyl diruthenium complexes (CR2)(EMe2)[(η5-C5H3)Ru(CO)2]2 (R = Me, H; E = Si, Ge)

“…Photolysis of the various dimeric Cp' 2 Ru 2 (CO) 4 complexes (such as Cp 2 Ru 2 (CO) 4 [33,34], (CH 2 )[(h 5 -C 5 H 4 )Ru(CO) 2 ] 2 [4,32], [13], and FvRu 2 (CO) 4 [35]) in the presence of RC^CR' results in products with different coordination modes. For example, reaction of Cp 2 Ru 2 (CO) 4 [35], which were produced respectively by the reactions of (SiMe 2 ) 2 [(h 5 -C 5 H 3 )Ru(CO) 2 ] 2 and FvRu 2 (CO) 4 with C 2 Ph 2 under UV radiation.…”

“…For example, reaction of Cp 2 Ru 2 (CO) 4 [35], which were produced respectively by the reactions of (SiMe 2 ) 2 [(h 5 -C 5 H 3 )Ru(CO) 2 ] 2 and FvRu 2 (CO) 4 with C 2 Ph 2 under UV radiation. These results show that complex 2 do have different reactivity towards C 2 Ph 2 from the respective nonbridged or singly bridged biscyclopentadienyl diruthenium analogues, which may be ascribe to the rigid and tensive doubly bridged ligand and unusually long RueRu bond in structure of 2, that restrict the coordination mode of ligand C 2 Ph 2 .…”