M6L14and M6L18Units in Early Transition Element Cluster Compounds

Perrin, Christiane

doi:10.1002/9783527618316.ch5e

Cited by 5 publications

(1 citation statement)

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“…These phases are, of course, not composed of only metallic elements, but there is little to no doubt that most examples with extended cationic networks are metallic (baring unexpected special electronic stabilities). The parents of this class are the longer known discrete clusters in binary phases such as (Ta 6 Cl 12 ) 2þ (Cl -) 2 and the like, 4,5 and this family can be extended to a considerable variety of Zr 6 (Z)Cl 12 nþ analogues when extra electrons and bonding are supplied by one of a considerable variety of interstitial atoms Z, group 8-12 transition metals in particular. 6 The last products exhibit significantly stronger bonding by virtue of the early-late-transition-metal combinations, 7 but substantially all are probably semiconductors because the characteristic clusters are isolated by layers of halide.…”

Section: New Intermetallic Classes Via the Reduction Or Oxidationmentioning

confidence: 99%

Exploratory Synthesis: The Fascinating and Diverse Chemistry of Polar Intermetallic Phases†This article is based on J. D. Corbett’s address upon receipt of the 2008 American Chemical Society’s F. Albert Cotton Award in Synthetic Inorganic Chemistry sponsored by the F. Albert Cotton Endowment Fund.

Corbett

2009

Inorg. Chem.

122

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Exploratory synthetic adventures regarding the inorganic chemistry of polar intermetallic phases have proven to be especially productive of novel compositions, new and unprecedented structures, and unusual bonding regimes. Reactions of diverse elements with widely different electronegativities allow the definition of two opposed classes of products: polycationic or polyanionic clusters or networks of metals paired with the corresponding monatomic anions or cations. These can be usefully viewed as intermetallic "salts", redox products of simpler neutral intermetallic systems but with widely different factors governing their stabilities. Thus, combinations of rare-earth metals alone or with late transition metals form a novel variety of polymetal network structures with relatively isolated telluride (or halide) spacer anions. Similarly, extensions of traditional Zintl phases of the alkali or alkaline-earth metals from the later p elements to the earlier triels, Ga-Tl especially, yield many new and elegant polyanionic structures. The substitution or addition of still earlier p or late d metal components produces still electron-poorer and more condensed polar intermetallic phases with increasingly delocalized bonding, higher coordination numbers, and more unusual structures and bonding. These discoveries have also led to new approaches: electronic tuning via band calculations to generate new families of quasicrystals and their crystalline approximants with their characteristic structural regimes and regularities. Gold as a substituent generates particularly novel bonding in arrays of mixed metals or polygold anionic networks.

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Section: New Intermetallic Classes Via the Reduction Or Oxidationmentioning

confidence: 99%

Exploratory Synthesis: The Fascinating and Diverse Chemistry of Polar Intermetallic Phases†This article is based on J. D. Corbett’s address upon receipt of the 2008 American Chemical Society’s F. Albert Cotton Award in Synthetic Inorganic Chemistry sponsored by the F. Albert Cotton Endowment Fund.

Corbett

2009

Inorg. Chem.

122

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Computational Methods: Transition Metal Clusters

Gautier¹,

Halet²,

Saillard³

2005

Encyclopedia of Inorganic Chemistry

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Cluster chemistry is dominated by structural aspects. Indeed, structure and bonding are strongly related to stability and properties, and cluster structures are particularly diverse and often complex. Thus, electron‐counting rules, which relate structure to electron count, have been the key to the development of cluster chemistry as a distinct area of chemistry. These rules have been set up progressively along time with the help of quantum chemistry. This article deals with the recent progress on transition metal and mixed main group/transition metal cluster chemistry arising from the contribution of modern computational theory to the rationalization of structures. This article focuses on “viable” species, i.e., molecules that are isolable under reasonable conditions and deals with the exploration of the limitations of the classical electron‐counting rules as well as the establishment of new rules for new structural types with the help of quantum chemical calculations.

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Computational Methods: Transition Metal Clusters

Gautier

Halet

Saillard

2011

Encyclopedia of Inorganic and Bioinorganic Chemistry

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M₆L₁₄and M₆L₁₈Units in Early Transition Element Cluster Compounds

Cited by 5 publications

References 50 publications

Computational Methods: Transition Metal Clusters

Computational Methods: Transition Metal Clusters

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