Syntheses, solid-state structures, solution behavior of hypervalent organobismuth(III) compounds [2-(Et2NCH2)C6H4] BiX3− and DFT characterization of [2-(Me2NCH2)C6H4] BiX3− [X = Cl, Br, I; n= 1–3]

[2‐{E(CH2CH2)2NCH2}C6H4]nBiX3–n (E = O, NMe; X = Cl, Br, I; n = 1–3) and [2‐(Me2NCH2)C6H4]BiBr2 – New Hypervalent Organobismuth(III) Compounds

“…one nitrogen atom is strongly coordinated to the bismuth atom [Bi(1)–N(1) 2.660(11) Å for 3 , 2.744(14) Å for 4 ] trans to the chlorine atom, whereas the second nitrogen atom displays a weaker interaction [Bi(1)–N(2) 3.095(11) Å for 3 , Bi(1)–N(3) 3.061(14) Å for 4 ] with its vector almost trans to a carbon atom. The interatomic distance for the N→Bi interaction trans to the halogen atom in 3 and 4 is longer than in [2‐(Me 2 NCH 2 )C 6 H 4 ] 2 BiCl [2.570(5) Å] 19, but close to that observed for the ethyl analogue [2‐(Et 2 NCH 2 )C 6 H 4 ] 2 BiCl [2.645(6) Å] 17. The N→Bi interaction trans to the carbon atom is considerably shorter than in the related triorganobismuthanes (see Table 1), but of the same magnitude as in [2‐( R 2 NCH 2 )C 6 H 4 ] 2 BiCl [3.047(5) Å for R = Me 19; 3.056(7) Å for R = Et 17].…”

“…the sum of covalent and van der Waals radii for nitrogen and bismuth; Σ r cov (Bi,N) 2.27 Å and Σ r vdW (Bi,N) 3.94 Å] 24 almost trans to a Bi–C bond [N(1)–Bi(1)–C(1a) 157.3(2)° and 156.3(1)° for 1 and 2 , respectively]. The Bi–N bond lengths are considerably longer than those reported for [2‐(Me 2 NCH 2 )C 6 H 4 ] 3 Bi [3.04(2)–3.11(3) Å] 23, a behavior, which could be attributed to combined electronic and steric effects of the morpholinyl/piperazinyl groups as was found for the related [2‐(Et 2 NCH 2 )C 6 H 4 ] 3 Bi [3.214(7) Å] 17. The coordination arrangement at the bismuth atom, taking into account the intramolecular N→Bi interactions, is distorted octahedral [( C,N ) 3 Bi core] and the compounds can be described as a hypervalent 14‐Bi‐6 species [25, 26].…”

“…The crystals of both compounds belong to the R ‐3 rhombohedral system and contain highly symmetric discrete molecules, with no further intermolecular interactions between heavy atoms. In both molecules 1 and 2 the bismuth atom resides on a threefold axis, which relates the three aryl substituents in a propeller‐like conformation similar to that found in [2‐( R 2 NCH 2 )C 6 H 4 ] 3 Bi ( R = Me 23, Et 17). The nitrogen atoms coordinate weakly to bismuth [Bi(1)–N(1) 3.170(7) Å for 1 and 3.211(5) Å for 2 , respectively; cf.…”

“…[2,4,6‐Ph 3 C 6 H 2 ]BiCl 2 14 or [2,6‐Mes 2 C 6 H 3 ]Bi X 2 ( X = Cl 15, Br 16). Another strategy is to use one pendant arm ligand such as 2‐(Me 2 NCH 2 )C 6 H 4 9 and 2‐(Et 2 NCH 2 )C 6 H 4 17, or “pincer” ligands like 2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 [9, 18] and 2,6‐[MeN(CH 2 CH 2 ) 2 NCH 2 ] 2 C 6 H 3 18. These ligands protect the bismuth atom not only sterically by increased coordination, but also reduce considerably the Lewis acidity and consequently the tendency for oligomerization.…”

“…These ligands protect the bismuth atom not only sterically by increased coordination, but also reduce considerably the Lewis acidity and consequently the tendency for oligomerization. Indeed, the monohalides [2‐(Me 2 NCH 2 )C 6 H 4 ] 2 Bi X ( X = Cl 19, Br, I 9), [2‐(Et 2 NCH 2 )C 6 H 4 ] 2 Bi X 17 and [2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 ] 2 BiCl 20 are monomeric. The corresponding dihalides usually exhibit low solubility in nonpolar solvents and for [2‐(Me 2 NCH 2 )C 6 H 4 ]BiCl 2 a dimer association was described in solid state 9.…”