Tris(1‐methyl‐imidazol‐2‐yl)phosphane Complexes of Pnictogen, Tetrel, and Triel Cations

Abstract

cations gallium indium nitrogen ligands pnictogens tetrelThe synthesis and characterization of salts with the generic formula [P(Im) M][OTf] (Im=1-methyl-imidazol-2-yl; M=P, As or Sb and x=3; M=Ge or Sn and x=2) are reported. In all cases, the cations adopt a cage structure with two chemically and energetically distinct apical lone pairs. In contrast, complexes of gallium and indium engage two P(Im) ligands resulting in a distorted octahedral geometry for the triel center in compounds of the generic formula [{P(Im) } M][OTf] (M=Ga or In). An assessment of the acidity and basicity of the new compounds is presented.

Definition of the tetrel bond

“…5d) 140 are double and quadruple charge-assisted σ–anion type tetrel bonds, respectively, but the Ge⋯O close contact, Fig. 5e, in the crystal of [C 12 H 15 GeN 6 P 2+ , C 4 H 8 O 2 , 2(CF 3 O 3 S − ), C 2 H 3 N] 141 is a multiple charge-assisted σ–lone-pair type tetrel bond. The Sn⋯Cl, Sn⋯N, Sn⋯Cl, and Sn⋯Br/Sn⋯π(arene) attractive contacts in crystals shown in Fig.…”

“…− ), C 2 H 3 N]141 is a multiple charge-assisted σ-lone-pair type tetrel bond. The Sn⋯Cl, Sn⋯N, Sn⋯Cl, and Sn⋯Br/Sn⋯π(arene) attractive contacts in crystals shown in Fig.5f-h, and j are charge-assisted tetrel…”

Pyramidal Dicationic Ge(II) Complexes with Homoleptic Neutral Pnictine Coordination: A Combined Experimental and Density Functional Theory Study

“…While the +4 oxidation state dominates for germanium, cationic complexes based upon the +2 oxidation state, carrying a Ge-based lone pair of electrons, have attracted significant interest and have also stimulated the development of a range of unusual new dicationic Ge­(II) coordination complexes. These have used a variety of ligand types, such as cryptands, crown ethers, − and tri- or tetra-aza macrocycles , that tend to encapsulate the metalloid ion, tetra-amines and isocyanides, as well as bulky acyclic ligands such as N-heterocyclic carbenes, and substituted imidazolyl ligands, − which provide some steric protection for the Ge­(II) ion. A small number of examples with smaller chelates, such as 2,2′-bipyridine (bipy), have also been described .…”

Coordination Chemistry of the Antimony(III) and Bismuth(III) Cations using Bis(α‐iminopyridine) as Ligand

“…[15] Venugopal et al has efficiently stabilized Bi(III) cationic species within hydridotris (3,5-dimethylpyrazolyl)borate forming zwitterionic compounds. [16] The tripodal tetradentate ligands such as tris(benzoimidazol)amine [17] or tris(2-pyridyl)phosphine and analogues [18] also efficiently coordinate to these positively charged pnictogen acceptors (B and C respectively). Very recently, Martin et al have reported the Sb(III) [19] and Bi(III) [20] cationic complexes introducing the redox-active diiminopyridine as ligand (D).…”