Stable homopolyatomic anions of the post-transition metals. "Zintl ions". The synthesis and structure of a salt containing the heptantimonide(3-) anion

Adolphson, Douglas G.; Corbett, John D.; Merryman, Don J.

doi:10.1021/ja00439a022

Cited by 99 publications

(40 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Interpretation of a three-dimensional Patterson map yielded the coordinates of the Pd, CI, and P atoms. P-C(9) 1.873 (8) Pd-C(4) 2.052 (8) C(l)-C(4) 1.548 (10) The superscript i refers to the atom at equivalent position 1 -x, 1 -y , 1 -z in this table and in Table IV. 120.4 (5) Cl'-Pd-C(4) 176.6 (2) P-C(1)4(4) 90.6 (4)…”

Section: Methodsmentioning

confidence: 99%

Metalation of a trialkylphosphine. Structure of bis(.mu.-chloro)bis[2-(di-tert-butylphosphino)-2-methylpropyl]dipalladium

Oliver¹,

Mullica²,

Milligan³

1982

Inorg. Chem.

View full text Add to dashboard Cite

The structure of [P~C~((~-BU)~PCM~~CH~)]~ has been determined by single-crystal X-ray diffraction techniques. The compound crystallizes in the monoclinic space group P 2 J c with a = 7.709 (2) A, b = 15.187 (5) A, c = 13.383 (4) A, / 3 = 105.77 (2)', V = 1507.9 A3, and Z = 2. The structure was refined to R = 0.037 (0.043 for R,) for the 1838 unique reflections with I 1 3.0u(I). Metalation of a tri-tert-butylphosphine ligand has produced a saturated Pd-P-C-C four-atom chelate ring. The coordination about the palladium atom is square planar with the chloride ions cis to each other. Selected metrical details are Pd-P = 2.209 (2) A, Pd-C(u) = 2.052 (8) A, Pd-Cl(trans to P) = 2.429 (2) A, and Pd-Cl(trans to C) = 2.474 (2) A. The bond lengths are discussed in terms of trans influences and strain in the chelate ring. Metalation results in severely distorted Pd-P-C and P-C-C angles. The steric bulk of the tertiary phosphine ligand is described with a "ligand profile".. IntroductionIntramolecular metalation of aryl-substituted tertiary phosphine ligands to form metal-carbon bonds has been studied extensively in recent yearsS2 The reaction is facilitated by formation of five-and six-membered chelate rings and depends on the steric bulk of the phosphine ligand. In contrast, only a few examples of metalation of purely aliphatic phosphines have been reported.,"Recently, Goel and Clark7-lo reported intramolecular metalations of tri-tert-butylphosphine complexes to form

show abstract

Section: Methodsmentioning

confidence: 99%

Metalation of a trialkylphosphine. Structure of bis(.mu.-chloro)bis[2-(di-tert-butylphosphino)-2-methylpropyl]dipalladium

Oliver¹,

Mullica²,

Milligan³

1982

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…B. Mg 2 Sn mit der Anti-CaF 2 -Struktur) im Gegensatz zu legierungsähnlichen Phasen [13] sowie von b) Polyanionen unter stark reduzierenden Bedingungen in flüssigem Ammoniak, die später als Zintl-Ionen bezeichnet wurden. [15] Die Bezeichnung aller dieser Verbindungsklassen mit Zintls Namen erfolgte nach dessen Tod.…”

Section: Introductionunclassified

Polyanionische Cluster und Netzwerke der frühen p-Metalle im Festkörper: jenseits der Zintl-Grenze

Corbett

2000

Angewandte Chemie

Self Cite

115

View full text Add to dashboard Cite

“…[11,12] The further distinction of the Zintl boundary (or Zintl border) was introduced by Laves [6,11] as the dividing line between what we chose to call the triel group (group 13, aluminum or gallium family, symbol Tr) and the tetrel group (group 14, silicon family, symbol Tt). [13] The border itself had been defined earlier by Zintl [14] as the left-hand limit on the periodic table for elements that allow the formation of 1) monoatomic (8-N) anions (Sb 3À , Sn 4À ,...) in saltlike structures of compounds richest in an active metal (for example Mg 2 Sn in the anti-(CaF 2 ) structure family) as opposed to alloylike phases, [13] and 2) polyanions under strongly reducing conditions in liquid ammonia that were later designated [15] as Zintl ions. All assignments of Zintls name to these categories occurred posthumously.…”

Section: Introductionmentioning

confidence: 99%

Polyanionic Clusters and Networks of the Early p-Element Metals in the Solid State: Beyond the Zintl Boundary

Corbett

2000

Angewandte Chemie International Edition

Self Cite

336

View full text Add to dashboard Cite

Reduction of p-element (post-transition) metals and metalloids by alkali metals leads to many salts containing polyatomic clusters or network anions of these elements. The earliest solvated examples were referred to as Zintl ions. Synthetic explorations have now established that many of the clusters can in fact be obtained from neat (solvent free) high-temperature reactions of binary to quaternary systems, particularly for the heavier tetrel (group 14) and triel (group 13) elements. Some synthetic tricks have also proven useful. Electronic guidelines such as Wade's rules, known to account well for other types of electron-deficient cluster bonding, are widely applicable to these compounds, but numerous hypoelectronic (electron-poor) trielide salts have also been discovered. These developments also extend to related infinite network structures and Zintl (valence) compounds. The Zintl boundary designation traditionally delineated the tetrel elements that form salts with the active metals from those of the triel and earlier elements that were once thought to generate only intermetallic phases. The distinction no longer seems appropriate, at least with regard to some alkali-metal compounds of the triel elements.

show abstract

Stable homopolyatomic anions of the post-transition metals. "Zintl ions". The synthesis and structure of a salt containing the heptantimonide(3-) anion

Cited by 99 publications

References 8 publications

Metalation of a trialkylphosphine. Structure of bis(.mu.-chloro)bis[2-(di-tert-butylphosphino)-2-methylpropyl]dipalladium

Metalation of a trialkylphosphine. Structure of bis(.mu.-chloro)bis[2-(di-tert-butylphosphino)-2-methylpropyl]dipalladium

Polyanionische Cluster und Netzwerke der frühen p-Metalle im Festkörper: jenseits der Zintl-Grenze

Polyanionic Clusters and Networks of the Early p-Element Metals in the Solid State: Beyond the Zintl Boundary

Contact Info

Product

Resources

About