Insertion reactions of GaCp*, InCp* and In[C(SiMe3)3] into the Ru-Cl bonds of [(p-cymene)RuIICl2]2 and [Cp*RuIICl]4

The first carbonyl free ruthenium/low valent Group 13 organyl complexes are presented, obtained by insertion of ER (ER = GaCp*, InCp*, InC(SiMe(3))(3)]) into the Ru-Cl bonds of (p-cymene)RuCl2]2, Cp*RuCl]4 and Cp*RuCl2]2. The compound (p-cymene)RuCl2]2 reacts with GaCp*, giving a variety of isolated products depending on the reaction conditions. The Ru-Ru dimers {(p-cymene)Ru}2(GaCp*)4(mu3-Cl)2] and the intermediate {(p-cymene)Ru}2(mu-Cl)2] were isolated, as well as monomeric complexes (p-cymene)Ru(GaCp*)3Cl2], (p-cymene)Ru(GaCp*)2GaCl3] and (p-cymene)Ru(GaCp*)2Cl2(DMSO)]. The reaction of Cp*RuCl]4 with ER gives "piano-stool" complexes of the type Cp*Ru(ER)3Cl](ER = InCp*, InC(SiMe3)3], GaCp*. The chloride ligand in complex can be removed by NaBPh4, yielding Cp*Ru(GaCp*)3]+BPh4]-. The reaction of Cp*RuCl2]2 with GaCp* however, does not lead to an insertion product, but to the ionic Ru(II) complex Cp*Ru(GaCp*)3]+Cp*GaCl3]-. The ER ligands in complexes 3, 5, 6, 7 and 8 are equivalent on the NMR timescale in solution due to a chloride exchange between the three Group 13 atoms even at low temperatures. The solid state structures, however, exhibit a different structural pattern. The chloride ligands exhibit two coordination modes: either terminal or bridging. The new compounds are fully characterized including single crystal X-ray diffraction. These results point out the different reactivities of the two precursors and the nature of the neutral p-cymene and the anionic Cp* ligand when bonding to a Ru(II) centre.