New Main-Group-Element-Rich nido-Octahedral Cluster System: Synthesis and Characterization of [Et₄N][Fe₂(CO)₆(μ₃-As){μ₃-EFe(CO)₄}₂]

Abstract

A series of clusters of the form [Et4N][Fe2(CO)6(μ3-As)}(μ3-EFe(CO)4)], where E is either P or As, were synthesized from [Et4N]2[HAs{Fe(CO)4}3] and ECl3. AsCl3 gives the As-only compound; PCl3 produces compounds having two As atoms with one P atom, or one As atom and two P atoms, and they can exist as two possible isomers, one of which is chiral. The As2P and AsP2 clusters cocrystallize, and their structure as determined by single-crystal X-ray diffraction is given along with the structure of the As-only cluster. Analytical data as well as density functional theory calculations support the formation and geometries of the new molecules.

Transition metal complexes of the naked pnictide elements

“…102 In addition to P3Co(triphos){W(CO)5}2, which has been structurally characterized, the Cr and Mo pentacarbonyl analogues have been prepared in 59% and 31% yields, respectively. 103 The latter arises from the reaction of PMo{N 104 There are several isomers possible for the mixed As3-xPx-containing compound but not all appear to be formed. There is a clear preference for As in the central position, and in that position it has a low negative charge, which is consistent with the lack of binding to another metal fragment.…”