Hexanuclear rhodium hydrido-carbonyl clusters

Abstract

Multinuclear n.m.r. studies (1 H,' H-{103Rh}, l3C, 13C-{103Rh), and lo3Rh) show that protonation of [Rh6(C0)15]2and [Rh6(C0)15C]2-at low temperatures gives [Rh,H(CO),,]-and [Rh6H(CO)15C]-which contain terminal and triangular face-bridging hydrides respectively; warming these solutions to room temperature results in loss of hydrogen and formation of [ Rhl 2(CO)30]2-and [ Rhl 2( CO), , ( C),], -respectively.

Molecular Intracage Chemistry: [Rh6(CO)15]2− in Zeolite NaX

“…[9,19] Thus, the peaks at d 258, 230, and 203 in the room-temperature spectrum ( Figure 1A) are attributed to rhodium carbonyls without hydride ligands. The reversible 16 ] 3À .…”

Condensation of Nickel–Carbonyl Clusters with Soft Lewis Acids: Synthesis and Characterisation of the {Cd2Cl3[Ni6(CO)12]2}3– Dimer

“…In fact, careful study of the course of the reaction after the addition of CdCl 2 ·2.5H 2 O in small portions to a solution of [Ni 6 (CO) 12 ] 2-indicates a more complex pathway. The first product formed is, in fact, the previously reported [Ni 9 (CO) 18 ] 2-anion, [17,18] which is the main species present in solution after the addition of ca.…”

“…the assembly of nickel clusters with Lewis acids. We report here our results on the oligomerisation of [Ni 6 (CO) 12 ] 2-with the soft Lewis acid CdCl 2 . …”

“…For instance, nickel displays only the first two species in the series [Ni 3n (CO) 6n ] 2-(n = 2, 3), [17,18] whereas several compounds were prepared and characterised in the [Pt 3n -(CO) 6n ] 2-(n = 2-10) series. [2] Therefore, self-assembly of [Ni 3n (CO) 6n ] 2-(n = 2, 3) units into 1D infinite wires seems unlikely owing to excessive electrostatic repulsion between anions, even if [Ni 6 (CO) 12 ] 2-in its [NMe 4 ] + salt gives rise to columnar stacks. [19] For this reason, we focused our attention on the possibility of building-up oligomeric species based on nickel MCC following the second route described above, i.e.…”

“…Moreover, several MCC aggregates close to or trespassing in the nanofield can be prepared, for instance by the fusion of two or more anionic clusters with a central core constituted by a single cation, for example {Hg[Os 10 C(CO) 24 ] 2 } 2-, [8] or cationic moieties, such as [H 2 Ru 12 Cu 6 Cl 2 (CO) 34 ] 2-, [9] [H 4 Ru 20 Cu 6 Cl 2 -(CO) 48 ] 4- [10] and [Ag 3 Ru 10 C 2 (CO) 28 Cl] 2-. [11] The existence in solution of several fused MCC moieties such as {Ag[Rh 6 C(CO) 15 ] 2 } 3-and higher {Ag n-1 [Rh 6 C(CO) 15 ] n } noligomers was demonstrated several years ago by multinuclear NMR spectroscopy, [12] and envisions the possibility to isolate MCC aggregates well beyond 2 nm. For instance, an [ infinite {[AgRu 6 C(CO) 16 ] -} ϱ superwire was quantitatively assembled by the reaction of [Ru 6 C(CO) 16 ] 2-with Ag + ions.…”