Metal cluster anions

Leopold D G, Ho J and Lineberger W C 1987 Photoelectron spectroscopy of mass-selected metal cluster anions. I. Cuji, n = 1 -10 J. Chem. Phys. 86 1715... 

Many of the metal cluster anions have been produced by cathode discharge in He doped with Ar and studied in a flow tube reactor. A few clusters have been prepared by laser vaporization using a supersonic cluster beam source and the reac-... 

Gas-Phase Metal Cluster Anions of Transition Metals, Production, and Gas-Phase Reactions... 

Platinum oxide cluster anions [Pt O]- and [PtM02] have been prepared by the reaction of the bare metal cluster anions [Pt ]- with N20 and 02, respectively (255). These platinum oxide cluster anions will oxidize CO to C02 and produce [PtJ, which can be reoxidized by N20 or 02. Thus a cyclic catalytic system for the oxidation of CO by N20 or 02 is produced. 

Photoelectron spectroscopy has been used to determine the threshold of electron detachment in small cluster anions and in some cases electronic transitions may be observed. The group of Nakajima and co-workers (261-264) studied several metal sulfide cluster anions. Many other systems have been studied by photoelectron spectroscopy including the [LaCJ (265), [AuC6F6] (266), and mixed-metal cluster anions (267). 

As mentioned in the Introduction, no structural information on these species was available for more than 40 years after the discovery of the first Zintl metal cluster anions, since no pure crystalline phases could be isolated and characterized structurally. Nevertheless, early efforts to rationalize the observed formulas and chemical bonding of these intermetallics and related molecules utilized the Zintl-Klemm concept [75, 76] and the Mooser-Pearson [77] extended (8 — N) rule. In this rule N refers to the number of valence electrons of the more electronegative metal (and thus anionic metal) in the intermetallic phases. 

Mingos rules. This hypoelectronicity or electron poverty (fewer than the Wade-Mingos 2n + 2 skeletal electrons) in the bare metal cluster anions Enz (z < n + 2) leads to deltahedra not only different from those in the deltahedral boranes but also different from those in hypoelectronic metal carbonyl clusters of metals such as osmium. 

Luetkens ML, Teixidor F, Rudolph RW (1984) Diheteronuclear and triheteronuclear metal cluster anions containing transition-metals. Inorg Chimi Acta 83 L13-L15... 

Metal cluster anions can be employed in place of the mononuclear metal carbonylate anions. Complexes that have been used include [Fe2(CO)8]2, 107 [Fe3(CO)n]2, 92,132 [Fe4(CO)13]2-,132 227233 [HRu3(CO)u]-,124,136,137... 

Neutron analysis of a five-coordinate H (/u. -H) atom has also been reported, located in two sqnare pyramidal positions of the [H2Rhi3(CO)24] metal cluster anion. As in the case of the Co-H series, a similar trend was noticed in Rh-H distances increasing as a function of the number of metal atoms around the H atom. 

Metal cluster anions are usnally stabilized in salts that contain large cations common choices are [Ph4P], [Ph As], Bu4N] and [(Ph3P)2N]. Compatibility... 

There have been numerous photodetachment studies of small cluster anions, and we now give some examples. Noble metal clusters (Cu, Ag,7, Au , n = 1-10) have been studied by Ho et al. [23], who resolved vibrations in all three dimers. Studies of alkali metal cluster anions have included those of Na ( = 2-5), K (n = 2-19), RbJ 3, and CS2-3 [24,25]. Carbon cluster anions C,T have photoelectron spectra that are consistent with linear chains for n = 2-9 and monocyclic rings for n = 10-29 [26]. Photoelectron spectra of Sb and Bi to n = 4 [27] show rich vibrational structure for the dimers, and the spectra of the larger clusters could be interpreted in terms of ab initio calculations. The threshold photodetachment (zero electron kinetic energy, ZEKE) spectrum of Si4 [28] shows a progression of well-resolved transitions between the ground state of the rhombic anion (Dzh, and vibrational levels of the first excited... 

Photoelectron Spectra of IVauisition Metal-Cluster Anions 130... 

Lerme, J., Dugourd, P., Hudgins, R.R., Jarrold, M.F., High-resolution ion mobiUty measurements of indium clusters electron spill-out in metal cluster anions and cations. Chem. Phys. Lett. 1999, 304, 19. 

An Ru-Re mixed-metal cluster anion with the formula [RuRe6G(GO)2i] was created from a photochemical reaction between the [Re6G(GO)i9] anion and Ru3(GO)i2- Heterometallic sulfide clusters of Ru-Re with open or cubane structures are also known. 

Leuchner, R. E. Harms, A. C. Castleman, A. W. Thermal metal cluster anion reactions Behavior of aluminum clusters with oxygen. J. Chem. Phys. 1989,91, 2753 Aluminum cluster reactions. 1991, 94, 1093. 

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