Organometallic Compounds with Homonuclear Bonds between Bismuth Atoms, 70 Years after Paneth' Report on the Violet Dimethyl Bismuth Compound

Abstract

The chemistry of organometallic compounds of the types (R 2 Bi) 2 , (RBi) n (n ϭ 2Ϫ5) and R 6 Bi 8 is the objective of this report. Common features and differences between these bismuthanes and Metallorganische Verbindungen mit homonuklearen Bindungen zwischen Bismut-Atomen, 70 Jahre nach Paneths Bericht über die violette Dimethylbismut-Verbindung Inhaltsübersicht. Die Chemie metallorganischer Verbindungen der Typen (R 2 Bi) 2 , (RBi) n (n ϭ 2Ϫ5) und R 6 Bi 8 ist Gegenstand dieses Berichts. Gemeinsamkeiten und Unterschiede zwischen diesen Bis-621 analogous compounds of lighter group 15 elements are discussed.

Bi−P Bond Homolysis as a Route to Reduced Bismuth Compounds and Reversible Activation of P4

“…The crystallographically distinct bismuth centers are pyramidal, with longer Bi−N bonds (2.194(3) Å and 2.199(3) Å) compared to those in 3 (2.153(3) Å and 2.130(3) Å), consistent with a reduced metal center. The Bi−Bi distance of 3.0201(2) Å is within the range recorded for dibismuthanes (2.990(2)–3.1821(3) Å), and shows only minor variation over the temperature range 100–293 K (3.0201(2) Å–3.0393(2) Å, Figure S10 in the Supporting Information). Intramolecular bismuth⋅⋅⋅oxygen contacts to the ligand on the opposing metal center (3.274(2) Å and 3.330(2) Å) may contribute to the stability of the Bi−Bi core of this molecule.…”

Reduction vs. Metathesis in the Reactions of Bismuth Tribromide with a Bulky Lithium Silanide – An Experimental and Theoretical Study

“…This is due to the increasing protection of the metal center in the molecules. Finally, such compounds with Bi–Bi bonds open a way to ring systems or to bismuth species in its +1 oxidation state, for example 31b. Sterically protecting ligands should play a key role and determine all probabilities of reaction of the complexes.…”

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

“…The inactivity of the bismuth lone pair in such species means that the metals are largely coordinated by the electrons in the double or triple Bi-Bi bond. The reactions of neopentyl- [126] and trimethylsilylmethyl-cyclobismuthanes [127] with the transition metal carbonyl compounds [Fe 2 (CO) 9 ] and [W(CO) 5 (THF)] lead to cyclic and side-on coordinated dibismuthane complexes, respectively [128][129][130] (Fig. 12) [135].…”