Metallocenes of Nb and Ta with η2-Se2H, SeH, and Se Ligands – Crystal Structures of [Cp′2Ta(SeH)H2] and [Cp′2Ta(=Se)H·W(CO)5] (Cp′ =tBuC5H4)

The reactions of [Cp#2NbBH4] (1) [Cp# = C5Me5 (Cp*) or C5Me4Et] and [Cp′2TaH3] (Cp′ = tBuC5H4) with elemental selenium give complexes of the general composition [Cp2MSe2H]. These exist in three isomeric forms, A–C, depending on the metal and the chalcogen. [Cp#2NbSe2H] (2) incorporates the novel η2-Se2H ligand (C), which is labile when exposed to light. Solutions of 2(Cp*) can be converted into [Cp*2NbSe2H] (3), which exists in two isomeric forms A or B, along with [Cp*2NbSe3H] (4) and [Cp*2NbO2H] (5). [Cp′2Ta(η2-Se2)H] (6) is the only isomer found for the Ta system. Se abstraction by means of P(OEt)3 gives [Cp′2Ta(=Se)H] (7). Complex 7 can be reduced with Na/Hg and subsequently hydrolysed …

Preparative and Electrochemical Investigations on the Electron Sponge Behavior of Cobalt Telluride Clusters: CO Substitution in[Co11Te7(CO)10]n− Ions (n=1, 2) by PMe2Ph and Crystal Structure of[Co11Te7(CO)5(PMe2Ph)5]

The reaction of the cluster salts [Cp* 2 Nb(CO) 2 ] n [Co 1 1 Te 7 (CO) 1 0 ] (Cp* = C 5 Me 5 ; n = 1, 2) with excess PMe 2 Ph gave the neutral, dark brown clusters [Co 1 1 Te 7 (CO) 6 (PMe 2 Ph) 4 ] (5) and [Co 1 1 Te 7 (CO) 5 (PMe 2 Ph) 5 ] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X+ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co 1 1 Te 7 ] core, but with a ligand sphere composed of five CO and five PMe 2 Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of C…

Bis(η-tert-butylcyclopentadienyl)hydridoniobium Ditelluride, a Convenient Reagent for the Synthesis of Polynuclear Metal Telluride Complexes

Metal Telluride Clusters Composed of Niobocene Carbonyl, Telluride, and Cobalt Carbonyl Units: Syntheses, Structures, and Reactivity

Abstract: The reaction of [Cp#2NbTe2H] (1#; Cp# = Cp* (C5Me5) or Cp(x) (C5Me4Et)) with two equivalents of [Co2(CO)8] gives a series of cobalt carbonyl telluride clusters that contain different types of niobocene carbonyl fragments. At 0 degrees C, [Cp#2NbTe2CO3(CO)7] (2#) and [Co4Te2(CO)10] (3) are formed which disappear at higher temperatures: in boiling toluene a mixture of [cat2][Co9Te6(CO)8] (5#) (cat= [Cp#2Nb(CO)2]+) and [cat2][Co11Te7(CO)10] (6#) is formed along with [cat][Co(CO)4] (4#). Complexes 6# transform into [cat][Co11Te7(CO)10] (7#) upon interaction with HPF6 or wet SiO2. The molecular structures of 2(Cp(x)), 4(Cp(x)), 5(Cp*), 6(Cp*) and 7(Cp*) have been determined by X-ray cr…