The two new anions [OsRh5(CO)16] (1) and [OsRh3(CO)12] (2) have been obtained, in a 1:1 mixture, by acidification of [OsRh4(CO)15]2-. Alternative synthetic routes have been devised: 1 may be also produced by condensation of Rh1 derivatives on [OsRh4(CO)15]2- or, more conveniently, with a one-pot synthesis, starting from Os3(CO)12 and Rh4(CO)12; 2 may be obtained by oxidative demolition of [OsRh4(CO)15]2 with iodine. Both anions were characterized by single-crystal X-ray diffraction of their [(Ph3P)2N]+ (PPN) salts. (PPN)[OsRh5(CO)16]: space group C2/c. Z = 8, a = 33.665 (4) Å, b = 9.752 (1) Å, c = 33.785 (5) Å, β = 94.45 (1 )°, R = 0.030, and Rw = 0.031 for 5166 independent reflections with I > 3σ(I). (PPN)[OsRh3(CO)12]: space group P21/c, Z = 4, a = 14.707 (3) Å, b = 21.371 (6) Å, c = 16.095 (3) Å, β = 102.83 (2)°, R = 0.037, and Rw = 0.037 for 3007 independent reflections with I > 3σ(I). Anion 1 shows a Rh6(CO)16-like structure with 12 terminal carbonyls (2 on each metal) and 4 triply bridging on the alternate faces of the octahedral skeleton. Anion 2 has a tetrahedral metal frame with an unprecedented ligand disposition, 7 terminal and 5 bridging carbonyls with overall C5 ideal symmetry. 13C NMR spectra in the temperature range 323-183 K evidenced a fluxional behavior in 2, from complete CO scrambling to a static situation consistent with the solid-state structure; compound 1 was found to be static at room temperature. © 1992 American Chemical Society.
|Titolo:||Mixed rhodium-osmium carbonyl clusters. Synthesis of the anions [OsRh5(CO)16]- and [OsRh3(CO)12]- and crystal structures of their (μ-nitrido)bis(triphenylphosphorus)(1+) salts|
SIRONI, ANGELO AGOSTINO DANIELE (Ultimo)
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||1992|
|Digital Object Identifier (DOI):||10.1021/ic00039a043|
|Appare nelle tipologie:||01 - Articolo su periodico|