The distinction between valence electrons and essentially inactive core electrons is the basis of many classifying concepts in chemistry. However, it has recently been recognized that this is an oversimplification and should, at least in some areas of chemistry, be modified. Many cases are known where cations with closed d10 configurations are subject to homoatomic interactions that influence structure and properties. A characteristic and surprisingly uniform structural feature (e.g., of a number of compounds containing monovalent coinage metals) is a clusterlike assembly of d10 cations that corresponds in geometry and bond lengths to fragments of the metal structures themselves. Further evidence for a special type of bonding in such compounds is provided by their physical properties; for example, the absorption in the UV/VIS region shows a drastic redshift and the compounds are often conductors or semiconductors. The d electrons in such cases have obviously lost their pure “core” nature. All bonding models so far proposed for such systems involve mixing of higher orbitals.

Homoatomic d10–d10 Interactions: Their Effects on Structure and Chemical and Physical Properties

Chemists today are increasingly fascinated by gold’s unique position in the family of elements. In this review, the author looks at important new results emerging from recent research in gold chemistry.

/pdf/the-fascinating-implications-of-new-results-in-gold-36yg0lunjg.pdf

The fascinating implications of new results in gold chemistry

In 2009, we reported C−halogen reductive elimination reactions from dinuclear Pd(III) complexes and implicated dinuclear intermediates in Pd(OAc)2-catalyzed C−H oxidation chemistry. Herein, we report results of a thorough experimental and theoretical investigation of the mechanism of reductive elimination from such dinuclear Pd(III) complexes, which establish the role of each metal during reductive elimination. Our results implicate reductive elimination from a complex in which the dinuclear core is intact and suggest that redox synergy between the two metals is responsible for the facile reductive elimination reactions observed.

/pdf/bimetallic-reductive-elimination-from-dinuclear-pd-iii-1ntelrt2bk.pdf

Bimetallic Reductive Elimination from Dinuclear Pd(III) Complexes

Solutions of K[Au(CN)(2)] and K[Ag(CN)(2)] in water and methanol exhibit strong photoluminescence. Aqueous solutions of K[Au(CN)(2)] at ambient temperature exhibit luminescence at concentration levels of > or =10(-2) M, while frozen methanol glasses (77 K) exhibit strong luminescence with concentrations as low as 10(-5) M. The corresponding concentration limits for K[Ag(CN)(2)] solutions are 10(-1) M at ambient temperature and 10(-4) M at 77 K. Systematic variations in concentration, solvent, temperature, and excitation wavelength tune the luminescence energy of both K[Au(CN)(2)] and K[Ag(CN)(2)] solutions by >15 x 10(3) cm(-1) in the UV-visible region. The luminescence bands have been individually assigned to *[Au(CN)(2)(-)](n) and *[Ag(CN)(2)(-)](n) excimers and exciplexes that differ in "n" and geometry. The luminescence of Au(I) compounds is related for the first time to Au-Au bonded excimers and exciplexes similar to those reported earlier for Ag(I) compounds. Fully optimized unrestricted open-shell MP2 calculations for the lowest-energy triplet excited state of staggered [Au(CN)(2)(-)](2) show the formation of a Au-Au sigma single bond (2.66 A) in the triplet excimer, compared to a weaker ground-state aurophilic bond (2.96 A). The corresponding frequency calculations revealed Au-Au Raman-active stretching frequencies at 89.8 and 165.7 cm(-1) associated with the ground state and lowest triplet excited state, respectively. The experimental evidence of the exciplex assignment includes the extremely large Stokes shifts and the structureless feature of the luminescence bands, which suggest very distorted excited states. Extended Huckel (EH) calculations for [M(CN)(2)(-)](n) and *[M(CN)(2)(-)](n) models (M = Au, Ag; n = 2, 3) indicate the formation of M-M bonds in the first excited electronic states. From the average EH values for staggered dimers and trimers, the excited-state Au-Au and Ag-Ag bond energies are predicted to be 104 and 112 kJ/mol, respectively. The corresponding bond energies in the ground state are 32 and 25 kJ/mol, respectively.

Excited-State Interactions for [Au(CN)2-]n and [Ag(CN)2-]n Oligomers in Solution. Formation of Luminescent Gold−Gold Bonded Excimers and Exciplexes

Homoatomare d10‐d10‐Wechselwirkungen — Auswirkungen auf Struktur‐ und Stoffeigenschaften

Geometrical isomers of [Ph2P(CH2)2AuX2]2: crystal and molecular structures of trans, trans-]Ph2P(CH2)2AuBr2]2 and cis, trans-[Ph2P(CH2)2AuCl2]2

Activation of two carbon-hydrogen bonds of nitromethane by a dinuclear gold(II) ylide complex. The formation of a CHNO2-bridged A-frame complex

Reaction of (Ph3P)2PtS4 with MeO2CCCCO2Me: synthesis and structure of (dimethyldimercaptomaleato(2−)-S,S′)bis(triphenylphosphine)platinum(II)

X-Ray Crystal and Molecular Structure of a Platinum(II) Complex Containing a PtS4Ring, [(C6H5)3P]2PtS4· CHCI3(Raumgruppe P21/ n; Diskussion der Bindungslängenund -winkel).

Experimental and Theoretical Studies of Dinuclear Gold(I) and Gold(II) Phosphorus Ylide Complexes.

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