Cage Extension to Clusters with Co₂/Co₃MoAs₆ Polyhedron Frameworks

Abstract

Good yields of the heteroatom clusters 1 and 2 were obtained by deliberate cage extension. The Co3MoAs6 polyhedral framework of 2 corresponds to a distorted sphenocorona. The ideal polyhedral sphenocorona with 10 corners, 14 faces, and 22 edges is shown right. Cp* = η5‐C5Me5.

Synthesis and Redox Chemistry of a Homoleptic Iron Arsenic Prismane Cluster

“…Amongst others, the group of Fenske succeeded in obtaining several hetero‐ and homometallic As 6 prismane clusters [{Cp R M} 3 (μ 3 ,η 4:4:4 ‐As 6 )] +n ( I – IV ; Cp R =Cp*, Cp + , Cp’, Cp’’; M=Fe, Co; n=0, 1, 2, Scheme 1) as well as their lighter P‐derivatives [{Cp * M} 3 (μ 3 ,η 4:4:4 ‐P 6 )] +n (M=Fe, Co; n=0, 1) from co ‐ thermolysis as well as salt metathesis reactions [10] . However, studies on their reactivity are scarce and limited to “Aufbau”‐reactions leading to extended heterotetranuclear clusters [11] . Yet, the redox chemistry of these compounds remains completely unstudied and no anionic arsenic prismane clusters could be isolated so far, which becomes even more of a target against the background of the wide range of skeletal electron numbers observed in the complexes mentioned above (Scheme 1).…”

“…[10] However, studies on their reactivity are scarce and limited to "Aufbau"reactions leading to extended heterotetranuclear clusters. [11] Yet, the redox chemistry of these compounds remains completely unstudied and no anionic arsenic prismane clusters could be isolated so far, which becomes even more of a target against the background of the wide range of skeletal electron numbers observed in the complexes mentioned above (Scheme 1).…”

Pn and Asn Ligands: A Novel Chapter in the Chemistry of Phosphorus and Arsenic

“…27 The complexes 32a and 33 serve as versatile starting materials for cluster expansion reactions. 28 The skeleton of [Pd 9 As 8 L 8 ] (L ) PPh 3 ), prepared by the reaction of [PdCl 2 L 2 ] with As(SiMe 3 ) 3 , is made up of a Pd-centered Pd 8 cube, capped by four As 2 units. Further illustrative examples of the often unpredictable E n and/or cluster-type complexes are the tetranuclear species 34 and 35, with nine and six pnictogen atoms, respectively (eqs 13 and 14).…”

“…Compounds of the type 32 have been examined by means of density functional calculations. 27 The complexes 32a and 33 serve as versatile starting materials for cluster expansion reactions . The skeleton of [Pd 9 As 8 L 8 ] (L = PPh 3 ), prepared by the reaction of [PdCl 2 L 2 ] with As(SiMe 3 ) 3 , is made up of a Pd-centered Pd 8 cube, capped by four As 2 units 26d…”