Sebastian Heinl

Activation of group 15 based cage compounds by [CpBIGFe(CO)2] radicals

The sterically encumbered dimer [CpBIGFe(CO)2]2 (1) (CpBIG = C5(4-nBuC6H4)5) is able to activate small tetrahedral molecules like P4 and As4 as well as the less reactive cage compounds P4S3 and P4Se3 at room temperature to give the products [{CpBIGFe(CO)2}2(μ,η1:1-cage)] (cage = P4 (2a), As4 (2b), P4S3 (2c), P4Se3 (2d)) in a quantitative manner. The reaction proceeds via selective cleavage of one E–E bond (E = P, As) of the starting material. Complex 1 also reacts with CS2 forming the binuclear compound [{CpBIGFe(CO)2}{CpBIGFeCO}(μ,η1:2-CS2)] (3).

Giant Spherical Cluster with I-C140 Fullerene Topology.

We report on an effective cluster expansion of CuBr-linked aggregates by the increase of the steric bulk of the CpR ligand in the pentatopic molecules [CpRFe(η5-P5)]. Using [CpBIGFe(η5-P5)] (CpBIG=C5(4-nBuC6H4)5), the novel multishell aggregate [{CpBIGFe(η5:2:1:1:1:1:1-P5)}12(CuBr)92] is obtained. It shows topological analogy to the theoretically predicted I-C140 fullerene molecule. The spherical cluster was comprehensively characterized by various methods in solution and in the solid state.

The Superbulky Pn Ligand Complexes [CpBIGFe(η5−P5)] and [(CpBIGFe)2(μ,η4:4-P4)]—Synthesis and Characterization

Abstract A new synthesis of [CpBIGFe(CO)2]2 3 (CpBIG = C5(4-nBuC6H4)5) was developed starting from CpBIGNa and FeCl2 in the presence of CO. Reaction of this product with P4 leads to the two new Pn ligand complexes [CpBIGFe(η5-P5)] 1b and [(CpBIGFe)2(μ,η4:4-P4)] (4) containing the highly sterically demanding CpBIG ligand. Depending on the solvent, different ratios of 1b:4 are obtained. The products 1b, 3, and 4 were characterized by spectroscopic methods as well as by X-ray diffraction. GRAPHICAL ABSTRACT

CpPEt2As4—An Organic‐Substituted As4 Butterfly Compound

CpPEt2 As4 (CpPEt =C5 (4-EtC6 H4 )5 ) (1) is synthesized by the reaction of CpPEt. radicals with yellow arsenic (As4 ). In solution an equilibrium of the starting materials and the product is found. However, 1 can be isolated and stored in the solid state without decomposition. As4 can be easily released from 1 under thermal or photochemical conditions. From powder samples of CpPEt2 As4 , yellow arsenic can be sublimed under rather mild conditions (T=125 °C). A similar behavior for the P4 -releasing agent was determined for the related phosphorus compound CpBIG2 P4 (2; CpBIG =C5 (4-nBuC6 H4 )5 ). DFT calculations show the importance of dispersion forces for the stability of the products.