Twelve One‐Electron Ligands Coordinating One Metal Center: Structure and Bonding of [Mo(ZnCH₃)₉(ZnCp*)₃]

Abstract

Surrounded by zinc: The reaction of [Mo(GaCp*)6] and Zn(CH3)2 zinc yields the exceptionally high‐coordinate title compound (see picture; Mo red, Zn green, C gray). Quantum chemical analysis reveals a unique bonding situation best described as a perfectly sd5 hybridized molybdenum atom with 12 valence electrons engaged in MoZn bonding. Another six electrons are delocalized over the Zn cage, evoking only weak ZnZn interactions.

Zn⋯Zn interactions at nickel and palladium centers

“…5 In particular, we came across this conceptual analogy in 2008 with the discovery of [Mo(ZnMe) 9 (ZnCp*) 3 ]. 6 This unique icosahedral coordinated complex can be regarded as a stable and accessible analogue of the matrix isolated polyhydride complex [WH 12 ], a species which, differently from the [MoZn 12 ] analogue, could better be written as [WH 6 (H 2 ) 3 ]. 7 The unique formation reaction of [Mo(ZnMe) 9 (ZnCp*) 3 ] is based on the chemistry of homoleptic compounds [M(GaCp*) n /2 ] ( n > 8; M = Mo, Ni, Pd, Pt, Cp* = pentamethylcyclopentadienyl) towards ZnMe 2 or ZnEt 2 , which leads to pseudo homoleptic all organo-zinc coordinated products with the general formula [M(ZnR) n ] ( n ≥ 8; M = Mo, Ru, Rh, Ni, Pd, Pt; R = Cp*, Et, Me).…”

Intermetalloid Clusters: Molecules and Solids in a Dialogue

“…[105] M/Zn intermetallics. [75,112,113] Notably,o nt he way towards all-zinc-ligated TM coordination compounds,G a/Zn mixed-shell intermediates of the general formula [M(GaR) n (ZnR) m ](R= Me,Cp*) were also isolated. [75,112,113] Notably,o nt he way towards all-zinc-ligated TM coordination compounds,G a/Zn mixed-shell intermediates of the general formula [M(GaR) n (ZnR) m ](R= Me,Cp*) were also isolated.…”

Intermetalloide Cluster: Moleküle und Festkörper im Dialog

“…Diesem synthetischen Grundprinzip folgend, konnte eine Anzahl hoch-koordinierter pseudo-homoleptischer Or [111] Diese Reaktionen verlaufen über eine redoxaktive Ligandensubstitution und beinhalten eine Reduktion von Zn II zu Zn I sowie die Oxidation von GaCp* zu Cp* x GaMe 3Àx und die Bildung von Decamethylfulvalen; dabei wird ein radikalischer Mechanismus angenommen. [75,112,113] Aufd em Wegh in zu zinkgebundenen Übergangsmetall-Koordinationsverbindungen wurden interessanterweise auch gemischtschalige Ga/Zn-Intermediate der allgemeinen Form [M(GaR) n (ZnR) m ]( R= Me,C p*) isoliert. [111,112] Obwohl auf den ersten Blick eine gewisse Verwandtschaft zu endohedralen Zintl-Ionen wie [Ir@Sn 12 ] 3À oder [Pt@Pb 12 ] 2À sinnvoll erscheint, suggerieren quantenchemische Rechnungen eine einzigartige,n icht-triviale Bindungssituation mit elektronendefizitären Mehrzentren-M-Zn-Bindungen sowie schwachen tangentialen Zn-Zn-Wechselwirkungen (vgl.…”