Reactions of Terphenyl-Substituted Digallene Ar^iPr₄GaGaAr^iPr₄ (Ar^iPr₄ = C₆H₃-2,6-(C₆H₃-2,6-ⁱPr₂)₂) with Transition Metal Carbonyls and Theoretical Investigation of the Mechanism of Addition

Abstract

ABSTRACT

Heterodiatomic Multiple Bonding in Group 13: A Complex with a Boron–Aluminum π Bond Reduces CO2

“…Unsurprisingly, therefore, multiple bonding in Group 13 was first achieved synthetically by one‐ and two‐electron reductions of diboranes and dialuminanes, populating their LUMO of E−E π‐bonding symmetry and affording mono‐ and dianionic doubly bonded species. Despite a slow start, the last decades have seen the advent of a number of neutral diborenes, diborynes, diboracumulenes, dialumenes, and digallenes . While the B−B multiple bonds, in analogy with their C, N, and O counterparts, are easily described by valence bond (VB) and molecular orbital (MO) theories, heavier analogues have been the subject of much discussion and speculation.…”

“…[10] Unsurprisingly,therefore,multiple bond-ing in Group 13 was first achieved synthetically by one-and two-electron reductions of diboranes [11][12][13][14] and dialuminanes, [15][16][17][18] populating their LUMO of EÀE p-bonding symmetry and affording mono-and dianionic doubly bonded species.D espite as low start, the last decades have seen the advent of an umber of neutral diborenes, [19][20][21][22][23] diborynes, [24][25][26] diboracumulenes, [27] dialumenes, [28] and digallenes. [29,30] While the BÀBm ultiple bonds,i na nalogy with their C, N, and Ocounterparts,are easily described by valence bond (VB) and molecular orbital (MO) theories, [31][32][33] heavier analogues have been the subject of much discussion and speculation. Thep roperties of these molecules have been discussed alternatively in the context of the Carter-Goddard-Malrieu-Trinquier model (CGMT), [34][35][36][37][38][39] of MO theory and of singlet biradicals.A ccording to the CGMT model, double bonding is increasingly described as the dimerization of singlet fragments upon moving down the group.This explains the distorted geometries,relative lability,and the observation of Wanzlick-type equilibria in these heavy compounds.…”

Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

“…We may view 6 as being composed by an Au(III) center coordinated to two [Co 2 (CO) 7 ] 2− anions (Figure 8), and its structure is reminiscent of [Au{Fe 2 (CO) 8 }] −[49]. The structure of the free anion [Co 2 (CO) 7 ] 2− has not been reported in the literature, but several of its adducts with main group and transition metals have been structurally characterized[50][51][52]. In agreement with the +3 oxidation state, the Au center is perfectly square planar.In contrast, 7 may be viewed as composed of an Au(I) center coordinated to two [Co 3 (CO) 9 ] − anions, acting as triply bridging ligands (Figure9).…”

Heterodiatomare Mehrfachbindung zwischen Elementen der Gruppe 13: Ein Komplex mit B‐Al‐π‐Bindung reduziert CO2

“…[10] Eine Mehrfachbindung konnte erstmalig synthetisch durch Ein-und Zweielektronenreduktion von Diboranen [11][12][13][14] oder Dialanen [15][16][17][18] realisiert werden. [29,30] Während B-B-Mehrfachbindungen analog zu den C-, N-und O-Systemen mit der Va lenzbindungs(VB)-und der Molekülorbital(MO)-Theorie beschrieben werden kçnnen, [31][32][33] waren Mehrfachbindungen der schweren Gruppe-13-Elemente Te il von großen Diskussionen und Spekulationen. Trotz des zähen Starts erbrachten die letzten Jahrzehnte einige neutrale Diborene, [19][20][21][22][23] Diborine, [24][25][26] Diboracumulene, [27] Dialene [28] und Digallene.…”

“…Trotz des zähen Starts erbrachten die letzten Jahrzehnte einige neutrale Diborene, [19][20][21][22][23] Diborine, [24][25][26] Diboracumulene, [27] Dialene [28] und Digallene. [29,30] Während B-B-Mehrfachbindungen analog zu den C-, N-und O-Systemen mit der Va lenzbindungs(VB)-und der Molekülorbital(MO)-Theorie beschrieben werden kçnnen, [31][32][33] waren Mehrfachbindungen der schweren Gruppe-13-Elemente Te il von großen Diskussionen und Spekulationen. Die Eigenschaften dieser Verbindungen wurden alternativ mit dem Carter-Goddard-Malrieu-Trinquier-Modell (CGMT), [34][35][36][37][38][39] der MO-Theorie und mit Singulett-Biradikalen erklärt.…”