[Rh₇(PiPr₃)₆H₁₈][BAr^F₄]₂: A Molecular Rh(111) Surface Decorated with 18 Hydrogen Atoms

Abstract

Heptarhodium wagon wheel [Rh7(PiPr3)6H18][BArF4]2 (shown), which resembles a planar Rh(111) surface with 18 hydride ligands, was obtained together with [Rh8(PiPr3)6H16][BArF4]2 from the reaction of [Rh(PiPr3)2(nbd)][BArF4] and [Rh(nbd)2][BArF4] with hydrogen (ArF=C6H3(CF3)2, nbd=norbornadiene). Some of the H ligands are located in threefold hollows between Rh centers and thus mimic the orientation of atomic hydrogen adsorbed on Rh(111).

A Carbene‐Rich but Carbonyl‐Poor [Ir6(IMe)8(CO)2H14]2+ Polyhydride Cluster as a Deactivation Product from Catalytic Glycerol Dehydrogenation

“…Originally, NMR spectroscopic data for 2 was unavailable because of its low yield (<1 %; see Table S1 in the Supporting Information), but its formation was enhanced by combining [Ir(IMe)(cod)Cl] or [{Ir(cod)(μ‐Cl)} 2 ] with [Ir(cod)(IMe) 2 ]BF 4 . Weller and co‐workers described a similar cluster synthesis from “naked” Rh and a Rh precursor 17. Screening (see Table S1) identified the best reaction conditions for the formation of 2 : The use of [Ir(IMe)(cod)Cl] raised the yield of 2 to approximately 12 %, with 2 and [Ir(IMe)(cod)Cl] present in a 1:1 ratio.…”

A ladder polysilane as a template for folding palladium nanosheets

“…Similar to 2, each Pd 7 nanosheet is supported by two silylene units in the plane and one silylyne moiety out of the plane; however, the array of Pd and Si atoms is different from that in 2 (vide infra). Three palladium atoms at the edge of the Pd 7 sheet are bonded to terminal isocyanide ligands, whereas five Pd atoms, Pd(1), Pd(5), Pd(6), Pd (7) and Pd (8), aligning in a slightly curved line are bound to four bridging isocyanide ligands (Fig. 2h).…”

“…These nanosheets suggest the possible preparation of transition metal nanosheets; however, the lack of precursors to which to apply mechanical separation suitable for isolation of monolayers prevents easy access to these compounds. The synthesis of relatively small transition metal nanosheets has attained some success in organometallic and inorganic chemistry [6][7][8][9] . Among them, a novel methodology to synthesize Pd 3 to Pd 5 nanosheets was developed by Murahashi et al [10][11][12][13][14][15][16] using (poly)cyclic aromatic hydrocarbons as a template for the arrangement of Pd atoms in a two-dimensional sheet structure.…”

“…The array of Pd and Si atoms and the dihedral angle of the two Pd 7 sheets are dependent on the substituent of the isocyanide ligand. 2 species between a Si-Si bond of oligosilanes to give complexes of the type (RNC) 2 Pd(SiR 3 ) 2 has been investigated extensively by Ito and coworkers 21,22 .…”

A Carbene‐Rich but Carbonyl‐Poor [Ir6(IMe)8(CO)2H14]2+ Polyhydride Cluster as a Deactivation Product from Catalytic Glycerol Dehydrogenation

“…The high N-heterocyclic-carbene (NHC) content is surprising, since reductive elimination of the imidazolium salt might have been expected. [17] Screening (see Table S1) identified the best reaction conditions for the formation of 2: The use of [Ir(IMe)(cod)Cl] raised the yield of 2 to approximately 12 %, with 2 and [Ir(IMe)(cod)Cl] present in a 1:1 ratio. [14a, 15, 16] Cluster formation from mononuclear metal-NHC precursors is unknown, but this cluster contains a record number of NHC ligands.…”