Coordination chemistry of stibine and bismuthine ligands

Neutral organoantimony(III) and organobismuth(III) ligands as acceptors in transition metal complexes – Role of substituents and co-ligands

“…As discussed above, species of the form SbR3 (triorganostibines) are generally considered as Lewis bases, and their donor behaviour towards transition metals has been well studied, 5,6,8 though the number of stibine complexes still represents a tiny fraction compared to number of phosphine complexes reported. Less well explored is their Lewis acidic character, which, while weak, allows the formation of long intra-or inter-molecular contacts, often referred to as 'hypervalent' interactions,  van der Waals radii for Sb and Bi are 2.47 and 2.54 Å, respectively.…”

“…1,[5][6][7][8] Halostibines and halobismuthines are expected to fall between the two extremes of Lewis acid and Lewis base behaviour due to the presence of both substituent types. Examples of these compounds acting as Lewis acids are rather rare and, unsurprisingly, complexes of ERX2, bearing two electronegative halide substituents, with other neutral ligands tend to be more prevalent than those with ER2X.…”

“…The coordination chemistry of triorgano-stibine and -bismuthine ligands has been reviewed previously, 5,6,7,8 whilst Braunschweig and co-workers have reviewed the synthesis, structure and properties of complexes containing a transition metal-bismuth bond. 9 Much of work relevant to the present article is quite disparate and has emerged only over the last decade and is not reviewed elsewhere.…”

Reactions of K2[Fe(CO)3(PPh3)]: Reductive Sb−Sb Coupling with Ph2SbCl To Form trans‐[Fe(CO)3(PPh3)(Sb2Ph4)] and Salt Metathesis with Me3SbCl2 To Yield trans‐[Fe(CO)3(PPh3)(SbMe3)]

“…While the analogous arsane and diarsane homologues exist in great numbers with similar structural motifs, analogous examples of antimony and bismuth species are much less common. [2,3] Weaker σ-donor and π-acceptor interactions in antimony and bismuth compounds may be a reason for this. Therefore, only monostibane and methylidene-bridged distibane complexes (X ϭ CH 2 ) obtained by substitution reactions, as in the case of phosphorus and arsenic compounds, have been structurally characterized.…”

Synthesis and Characterization of a Gold Complex Containing [SbPh]2– and [SbPh2]– Anions as Bridging Ligands

“…[6][7][8][9][10][11][12] However, gold complexes containing heavier group 15 elements are scarce. Recently, Au-As cluster complexes [13,14] were obtained by the synthesis of silylated arsines with Au I phosphane complexes and a few Au I complexes with tertiary ligands of the type ER 3 (E = Sb, Bi; R = organic group) are known for antimony, [15][16][17] but none for bismuth. [18] Only recently, the first Au I 2 ] with a M···Bi interaction (M = Cu, Bi) were reported.…”