Encapsulation of the transition metals chromium through cobalt in zirconium cluster iodides

Hughbanks, Timothy; Rosenthal, Guy L.; Corbett, John D.

doi:10.1021/ja00213a025

Cited by 67 publications

(45 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The data at 1 T give 1.05 BM over 100-300 K. These are below the ideal spin-only value of 1.73 BM for one unpaired electron, but this difference could well result from spin-orbital coupling with such heavy cluster elements. This sort of behavior has been analyzed for a Mn-centered zirconium cluster chloride (18). The boundaries of the electron exchange frequency between 17-and 18-e clusters are not evident with present data, nor is any notion of whether this freezes out to produce an ordered superstructure at some lower temperature.…”

mentioning

confidence: 57%

Two New Examples for the Unusual R12I17Z2-Structure Type: La12I17Fe2and Ce12I17Mn2

Lulei

Martin

Corbett

1996

Journal of Solid State Chemistry

Self Cite

View full text Add to dashboard Cite

mentioning

confidence: 57%

Two New Examples for the Unusual R12I17Z2-Structure Type: La12I17Fe2and Ce12I17Mn2

Lulei

Martin

Corbett

1996

Journal of Solid State Chemistry

Self Cite

View full text Add to dashboard Cite

“…expectations and the nature of the Zr -Z bonding. The former are relatively straightforward, as shown in Figure 7 for the charge-consistent result of iron in an idealized octahedral Zr6I'8 cluster of typical dimensions (Hughbanks, Rosenthal & Corbett, 1988). Symmetry properties alone mean that the t, u and t2g cluster-based states exchange functions relative to main-group Z, the t?g set now becoming Zr -Z bonding via Fe 3d orbitals while t, u 6 is the probable HOMO.…”

Section: Bonding In Clustersmentioning

confidence: 98%

“…By far the greater number of discrete clusters and structure types and therefore systematics originate with zirconium systems, particularly for the chlorides (Ziebarth & Corbett, 1985, 1989aZhang & Corbett, 1991 a) and iodides (Smith & Corbett, 1985Hughbanks, Rosenthal & Corbett, 1988). The rare-earth elements are in contrast the only sources of condensed cluster chain phases while both group 3 and group 4 metals afford infinite sheet products (section 8).…”

Section: Interstitials In Clustersmentioning

confidence: 99%

Structural and Bonding Principles in Metal Halide Cluster Chemistry

Corbett

1992

Modern Perspectives in Inorganic Crystal Chemistry

Self Cite

View full text Add to dashboard Cite

ABSTRACT. Metal cluster halides M6X'2 and M'6Xa and their alkali metal derivatives exhibit a variety of structure types because of the evident need to bond terminal or shared halide at all metal vertices. The versatility of systems with group 3 and 4 transition metals is greatly increased by the presence of interstitial heteroatoms (Z) within all thermodynamically stable clusters. The 24 examples of Z provide a wide range of valence electrons and include many that are themselves metals. Structural and bonding principles are described, including the novel characteristics of some cation sites, the regular effects that cations have on cluster bond distances, matrix effects that arise because of characteristic X··X or M -X distances and their influence on metal -metal bonding and electronic configurations, and the use of metal -metal hnl'1d orders to characterize matrix effects. The condensation products of octahedral clusters, particu:arly chains centered by heterometals and double-metal sheet products, are also noted. Condensation to ClustersThe clustering of two to six (or more) metals within a nonmetal matrix is a frequent event among reduced compounds of the early transition (d) elements. The formation of such clusters is probably best known among the chalcogenides, while only a relatively few halide examples were known for Nb, Ta and Mo 10-15 years ago. The relative proportion of anions for a fixed oxidation state of a metal obviously increases in the series pnictide, chalcogenide, halide (e.g., Vp, V 2 S 3 , VCI 3 ), and so the number of possible metal-metal interactions decrease in parallel. Thus, highly reduced pnictides and chalcogenides often exhibit condensed, complex, and relatively isotropic structures, whereas halides more often show limited and lower dimensional interactions between the valence-active metals, i.e., in isolated clusters and chains. The latter characteristics not only provide very novel results but also make more evident many of the bonding and structural principles that go into the determination of cluster and condensed cluster structures. Much of the background to this area can be found in Schafer and Schnering (1964) and Wells (1984).The beginning of metal-metal bonding is often seen structurally whenever the stoichiometric number of nonmetals (halides) per metal in a reduced compound is less than the preferred coordination number so that coordination polyhedra must be shared. Thus, ZrI4 achieves CN6 by sharing two edges of each ZrI6 octahedron, viz, ZrI 2 1 4/2 . Only when valence electrons are available does this allow 27 E. Parthe (ed.).

show abstract

“…The bromide appears to exhibit some clear matrix effects relative to the chloride beryllide; short intracluster Br3-Br7 and Br8-Br8 distances of 3.496 (2) (26)) halide systems. The preparation of a series of AZr Br Z phases, A"Li-Cs, Z"B, C, Mn is as expected from the chlorides already known, yet contrasting with the iodides where the A range is limited (23,27,28). The LiZr Br B member affords another, rare example of a structural change in which a small A cation is placed in an alternate site.…”

Section: Other Zirconium Bromides With Known Structuresmentioning

confidence: 82%

Comparative Zirconium Bromide Cluster Chemistry. A New Structure in K4Zr6Br18C

Corbett

1998

Journal of Solid State Chemistry

View full text Add to dashboard Cite

Encapsulation of the transition metals chromium through cobalt in zirconium cluster iodides

Cited by 67 publications

References 0 publications

Two New Examples for the Unusual R12I17Z2-Structure Type: La12I17Fe2and Ce12I17Mn2

Two New Examples for the Unusual R12I17Z2-Structure Type: La12I17Fe2and Ce12I17Mn2

Structural and Bonding Principles in Metal Halide Cluster Chemistry

Comparative Zirconium Bromide Cluster Chemistry. A New Structure in K4Zr6Br18C

Contact Info

Product

Resources

About