Reactivity of ytterbium in liquid ammonia

Abstract

1789 evacuation, and thawing to a residual pressure of 10 -J Tort: the tube was filled with argon, sealed, and kept at 120 ~ for 6 h. The polymer that formed was precipitated with ethanol and dried to constant weight.The authors express their gratitude to V. P. Nefedov and T. A. Zyablikova for the investigations of the reaction mixture by GC and ~H NMR spectroscopy. Referencesl. V. V. Ershov, G. A. Nikiforov, and A. A. Voiod "kin, Khimiya prostranstvenno-zatrudnennykh fenolov [Chemistry of Steri-cally ttindered Phenols], Khimiya, Moscow, L972 (in Russian). 2. USSR Invention Certificate No. 819078, Byul. Izobret., A solution of metallic ytterbium in liquid ammonia reacts readily with various carbonyl complexes of metals to form the corresponding Ianthanide carbonylmetallates. The reaction of an excess of Yb in liquid NH 3 with [CpFe(CO)2]2 gave (THF)4Yb[Fe(CO)2CP] 2 in 42% yield. It was suggested that the resulting complex contains two equivalent Yb--Fe bonds.

Recent chemistry of the η5-cyclopentadienyl dicarbonyl iron anion

“…A subsequent IR spectrum revealed absorptions for carbonyl ligands with stretching frequencies of 1934 and 1860 cm −1 . The authors conclude that the salt contained two equivalent Yb-Fe bonds, and the Yb is not coordinated with the bridging carbonyl ligands [55]. Ellis and Flom, originators of the aforementioned NaK 2.8 alloy method, found in 1975 that a KFp solution in THF readily reacted with n-tetrabutylammonium perchlorate to form the [(n-Bu) 4 N]Fp salt in 92-95% yields.…”

Lanthanide−Transition-Metal Carbonyl Complexes. 1. Syntheses and Structures of Ytterbium(II) Solvent-Separated Ion Pairs and Isocarbonyl Polymeric Arrays of Tetracarbonylcobaltate

“…Of the three structural possibilities, the most extensive class includes compounds possessing an isocarbonyl linkage between the metals . Compounds with a direct lanthanide−transition-metal bond are uncommon, and the unique metal−metal bond has been confirmed in only a few instances by single-crystal X-ray diffraction. , Another heterometallic category is characterized by a solvent-separated ion pair relationship, which has a lanthanide cation isolated from the transition-metal carbonylate anion by a coordinating solvent. 1m, Complexes in these three categories offer the possibility of functioning as catalyst precursors. 1e,k,, For instance, this laboratory has been employing {(DMF) 10 Yb 2 [Pd(CN) 4 ] 3 } ∞ as a heterogeneous bimetallic catalyst precursor in the reduction of NO x by CH 4 in the presence of O 2 and in the selective vapor-phase hydrogenation of phenol into cyclohexanone …”

Structures of DMF solvated potassium and sodium salts of [Fe(CO)4]2− and [M2(CO)8]2− (M = Fe, Ru)

“…1a). This kind of interaction was first noticed by Bau et al in complexes K 2 Fe(CO) 4 and Na 2 Fe(CO) 4 ,1.5(C 4 H 8 O 2 ) [7]. It differs from the known interactions such as direct metalemetal bonds, solvent-separated ion pairs, and isocarbonyl linkages between metal carbonyl anions and transition metal or lanthanide cations.…”

“…In addition, a "novel and not easily rationalized" interaction between alkali metals and carbonyl anion was first observed by Bau et al in the solid-state structures of solvent-free K 2 [Fe(CO) 4 ] and the dioxane solvated of Na 2 [Fe(CO) 4 ],1.5(C 4 H 8 O 2 ) [7]. This unique interaction along with the isocarbonyl linkages interaction led to the formation of extended three-dimensional structures.…”

“…These interactions are highly reliant upon the relative nucleophilicity of the metal; Lewis basicity of the carbonyl, and the coordinating ability of the solvent [3]. If the metal center in the carbonylate anion is the most nucleophilic constituent, a direct metalemetal bond forms [4]. When the electron-imparting ability of the solvent exceeds that of the carbonylate anion, solvent-separated ion pairs are generated [5].…”