The homoleptic group 5c arbonylates [M(CO) 6 ] À (M = Nb, Ta)s erve as ligands in carbonyl-terminated heterobimetallic Ag m M n clusters containing 3t o1 1m etal atoms. Based on our serendipitous [Ag 6 {Nb(CO) 6 } 4 ] 2 + (4a 2 +)p recedent, we established accesst os uch Ag m M n clusters of the composition [Ag m {M(CO) 6 } n ] x (M = Nb, Ta ; m = 1, 2, 6; n = 2, 3, 4, 5; x = 1À,1+ ,2+). Salts of those molecularc luster ions were synthesized by the reaction of [NEt 4 ][M(CO) 6 ]and Ag[Al(OR F) 4 ](R F = C(CF 3) 3)i nt he corrects toichiometry in 1,2,3,4tetrafluorobenzene at À35 8C. The solid-state structures were determined by single-crystal X-ray diffractionm ethods and, owing to the thermali nstability of the clusters, al imited scope of spectroscopicm ethods. In addition, DFT-based AIM calculations were performed to provide an understanding of the bonding within these clusters. Apparently,t he clusters 3 + (m = 6, n = 5) and 4 2 + (m = 6, n = 4) are superatom complexes with trigonal-prismatic or octahedral Ag 6 superatom cores. The [M(CO) 6 ] À ions then bind through three CO units as tridentate chelate ligands to the superatom core, giving overall structures related to tetrahedral AX 4 (4 2 +)o rt rigonal bipyramidal AX 5 molecules (3 +).
The unsubstituted acenium radical cations (ARCs) are extremely sensitive and were hitherto only studied in situ, i. e. in the gas phase, as dilute solutions in strong acids or by matrix isolation spectroscopy at about 10 K. In this study, room temperature stable ARC salts with the weakly coordinating anion [F{Al(OR F ) 3 } 2 ] À (OR F =À OC(CF 3 ) 3 ) supported by the weakly coordinating solvent 1,2,3,4-tetrafluorobenzene (TFB) were prepared and structurally, electrochemically and spectroscopically characterized. Reaction of the neutral acenes with Ag + [F{Al(OR F ) 3 } 2 ] À led, non-innocent, [54] to intermediate [Ag 2 (acene) 2 ] 2 + complexes, which decompose over time to Ag 0 and the corresponding (impure) ARC salts. By contrast, direct deelectronation with the recently developed innocent [54] deelectronator radical cation salt [anthracene Hal ] + • [F{Al-(OR F ) 3 } 2 ] À led to phase-pure products [acene] + • [F{Al(OR F ) 3 } 2 ] À (anthracene Hal = 9,10-dichlorooctafluoroanthracene; acene = anthra-, tetra-, pentacene). For the first time, a homogenous set of spectroscopic data on analytically pure ARC salts was obtained. In addition, cyclovoltammetric measurements of the acenes connected the potentials in solution with those in the gas-phase. Hence, the data complement the existing isolated gas-phase, strong acid or matrix isolation studies. A first entry to follow-up chemistry of the acenium radical cations as ligand forming oxidizers was demonstrated by reaction with 1 = 2 Co 2 (CO) 8 giving [Co(anthracene)(CO) 2 ] + .
Anything is possible! The cover depicts a scenario in ancient Egypt, with two construction masters considering possibilities for pyramids and invent a new method using [M(CO)6]– and Ag+ as building blocks for pyramids, columns, and arches. Even an impressive bipyramid didn't discourage them. The [M(CO)6]‐fragments serve as ligands in the obtained [Agm{M(CO)6}n]x‐clusters (M=Nb, Ta; m=1, 2, 6; n=2, 3, 4, 5; x=1–, 1+, 2+), DFT based AIM calculations were performed to provide an understanding of the bonding situation and the cores of the cations were interpreted as superatoms. More information can be found in the Full Paper by I. Krossing et al. on page 12373.
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