Synthesis and structural characterization of [N(PPh3)2][H2Ru3Rh(CO)12]

The mixed-metal carbonyl cluster anion [Ru3Ir(CO)13]−: synthesis, molecular structure, fluxionality, reactivity †

“…The IR spectrum of 3 shows five vibrations for terminal carbonyl groups and two absorptions indicating bridging CO ligands (Table 1), the pattern being similar to that of the structurally characterized complex [H 2 Ru 3 Rh(CO) 12 ] Ϫ . 15 The 1 H NMR spectrum of 3 shows a multiplet centred at δ 7.55 for the [N(PPh 3 ) 2 ] ϩ cation and a sharp singlet at δ Ϫ20.64 corresponding to the two equivalent hydride ligands. The hydride resonance does not change over a temperature range of 20 to Ϫ55 ЊC.…”

“…6 Accordingly, the tetrahedral The reaction of [Ru 3 Ir(CO) 13 ] Ϫ 1 with molecular hydrogen under refluxing conditions leads, with loss of one CO ligand, to the anionic dihydrido cluster [H 2 Ru 3 Ir(CO) 12 ] Ϫ 3 (Scheme 1), which is isoelectronic with the known cobalt and rhodium clusters [H 2 Ru 3 Co(CO) 12 ] Ϫ 14 and [H 2 Ru 3 Rh(CO) 12 ] Ϫ . 15 Thus, the new cluster anion 3 is accessible in the same way as the known cobalt homologue, whereas the rhodium homologue has been prepared by a different method, starting from [HRu 3 (CO) 11 ] Ϫ and [Rh(CO) 4 Cl 2 ]. 15 Anion 3 can be isolated as the bis(triphenylphosphoranylidene)ammonium salt in good yields giving brown-yellow air-stable crystals, which are soluble in polar and non-polar organic solvents such as thf, diethyl ether, dichloromethane or methanol.…”

“…15 Thus, the new cluster anion 3 is accessible in the same way as the known cobalt homologue, whereas the rhodium homologue has been prepared by a different method, starting from [HRu 3 (CO) 11 ] Ϫ and [Rh(CO) 4 Cl 2 ]. 15 Anion 3 can be isolated as the bis(triphenylphosphoranylidene)ammonium salt in good yields giving brown-yellow air-stable crystals, which are soluble in polar and non-polar organic solvents such as thf, diethyl ether, dichloromethane or methanol. The IR spectrum of 3 shows five vibrations for terminal carbonyl groups and two absorptions indicating bridging CO ligands (Table 1), the pattern being similar to that of the structurally characterized complex [H 2 Ru 3 Rh(CO) 12 ] Ϫ .…”

“…The Ru(1)᎐Ru(2) and Ru (2) 3 Ru H (2)᎐Ru (3)᎐C (9), whereas the non-bridged edge forms an Ru (2)᎐Ir (1)᎐C (4) Ϫ anion. 15 In the Ir (1)᎐Ru (1)᎐Ru (3) triangle, each metal atom carries two terminal carbonyl ligands and is involved in two carbonyl bridges, each metal-metal bond being almost symmetrically bridged by a CO ligand. Atom Ru(2) carries only three terminal carbonyl groups.…”

The chemistry of hydridocarbonylferrates revisited: syntheses and structures of the new [H2Fe4(CO)12]2− and [HFe5(CO)14]3− anions, and the [Fe(DMF)4][Fe4(CO)12(μ5-η2-CO)(μ-H)]2 adduct containing an unprecedented isocarbonyl

“…6 It must be remarked that the heavier Ru and Os congeners display a much richer cluster chemistry which includes species with nuclearity up to 20, e.g. [H 2 -n Os 5 (CO) 15 ] n-(n = 0-2), 7 Os 5 (CO) 16 , 8 Os 6 (CO) 18 , 9 Os 7 (CO) 21 , 10 Os 8 (CO) 23 , 11 [H 4 Os 10 (CO) 24 ] 2-, 12 [Os 17 (CO) 36 ] 2-, 13 and [Os 20 (CO) 40 ] 2-. 14 As a result of our ongoing interest in the chemistry of carbonylferrates and hydridocarbonylferrates, we herein report on the synthesis and X-ray structure of the [H 2 Fe 4 (CO) di-hydride di-anion, quantitatively obtained by protonation of [HFe 4 (CO) 12 ] 3in DMSO, as well as the serendipitous isolation and structural characterization of the new pentanuclear [HFe 5 (CO) 14 ] 3mono-hydride tri-anion.…”