Tris(benzoimidazol)amine (L) complexes of pnictogen(iii) and pnictogen(v) cations and assessment of the [LP]³⁺/[LPF₂]³⁺ redox couple

Abstract

A tris((1-ethyl-benzoimidazol-2-yl)methyl)amine (BIMEt3) complex of P3+ is oxidized with XeF2 to access [PF2(BIMEt3)]3+ representing the first structurally characterized example of a phosphorus(v)3+ cation.

On Transannulation in Azaphosphatranes: Synthesis and Theoretical Analysis

“…In the absence of a Lewis acid, a complex mixture was obtained in that synthesis, which was attributed to fluoride attacking phosphorus when the equatorial substituents were methyl or isopropyl groups. A similar phenomenon was observed when a tris­(benzimidazole) variant of Verkade’s base was oxidized to the difluorophosphorus­(V) complex in the presence of XeF 2 . In this work, we have isolated the bifluoride (HF 2 – ) salt of [FP­( i -BuNCH 2 CH 2 ) 3 N] + by direct treatment of the corresponding proazaphosphatrane with XeF 2 .…”

“…A similar phenomenon was observed when a tris(benzimidazole) variant of Verkade's base was oxidized to the difluorophosphorus(V) complex in the presence of XeF 2 . 27 In this work, we have isolated the bifluoride (HF 2 − ) salt of [FP(i-BuNCH 2 CH 2 ) 3 N] + by direct treatment of the corresponding proazaphosphatrane with XeF 2 . 28 The complex 1-F + was structurally characterized (Figure 1, left), revealing that the compound has a transannular distance similar to that of its methyl analogue: 1.920(1) Å for i-Bu; 1.932(3) Å for Me.…”

Tweaking the Charge Transfer: Bonding Analysis of Bismuth(III) Complexes with a Flexidentate Phosphane Ligand

“…The goal of the present study is to gain more insight into the bonding situation in bismuth­(III) complexes with the PS 3 ligand. Although other multidentate ligand systems are known in the literature, − due to their accordion-like structural flexibility the molecular skeleton of type PS 3 BiX 3 seems to be suitable for experimental investigations. First, we aim to predict computationally how the pnictogen interaction between the bridgehead atoms P and Bi observed in the neutral PS 3 BiX 3 compounds can be shifted into a dative (covalent) regime, and subsequently, we provide experimental evidence based on X-ray crystallography and NMR studies.…”

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

“…Worth mentioning, the reported antimony(III) di-cationic complexes have all triflate counter anions located within the sum of SbÀ O van der Waal's radii exhibiting weak interactions between them. [17] Compound 5 forms a distorted octahedral geometry, where the four nitrogen centers are in the distorted plane and the chloride and triflate anions occupy the axial sites, analogous to the structure of compound 1. The Sb-N im bond lengths are similar (Sb1-N2 = 2.2869( 17) and Sb1-N3 = 2.2464( 17) Å) to those observed in the case of 1.…”

“…[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).…”