Synthesis and Structure of (N,)C,N‐chelated Organoantimony(III) and Bismuth(III) Cations and Isolation of Their Adducts with Ag[CB₁₁H₁₂]

Abstract

The treatment of N,C,N-chelated antimony(III) and bismuth(III) chlorides [C 6 H 3 -2,6-(CH=NR) 2 ]MCl 2 [R = tBu and M = Sb (1) or Bi (2); R = Dmp and M = Sb (3) or Bi (4)] (Dmp = 2,6-Me 2 C 6 H 3 ) with one molar equivalent of Ag[CB 11 H 12 ] led to a smooth formation of corresponding ionic pairs {[C 6 H 3 -2,6-(CH=NR) 2 ]-MCl} + [CB 11 H 12 ] -[R = tBu and M = Sb (7) or Bi (8), R = Dmp and M = Sb (9) or Bi (10)]. Similarly, the reaction of C,N-chelated analogues [C 6 H 2 -2-(CH=NDip)-4,6-(tBu) 2 ]MCl 2 [M = Sb (5) or Bi (6), Dip = 2Ј,6Ј-iPr 2 C 6 H 3 ] gave compounds {[C 6 H 2 -2-(CH=NDip)-4,6-(tBu) 2 ]MCl} + [CB 11 H 12 ] -[M = Sb (11) or Bi (12)]. All compounds 7-12 were characterized with 1 H, 11 B and 13 C{ 1 H} NMR spectroscopy, * Prof. Dr. L. Dostál E-Mail: libor.dostal@upce.cz [a] ARTICLE nation number of the central atoms by replacing one of the donor pendant arms with tBu group. (13): Compound 7 (68 mg, 0.1 mmol) was dissolved in CH 2 Cl 2 (10 mL) and added to a solid sample of Ag[CB 11 H 12 ] (31 mg,

Neutral and Cationic β-Ketoiminato Bismuth Complexes

“…While the Bi–N distances in 2 vary from 2.598 to 2.759 Å, the Bi–O distances are in the range of 2.095 to 2.172 Å. The Bi–N distances are larger than the typical covalent Bi–N distances (2.19 Å, from the sum of covalent radii) reported in the literature and resemble to those observed in Bi–N dative bonds . The Bi–O distances correspond to a covalent bond (2.14 Å, from the sum of covalent radii), typically observed in alkoxo and aryloxo bismuth compounds …”

The reactivity of antimony and bismuthN,C,N-pincer compounds toward K[BEt3H] – the formation of heterocyclic compoundsvs. element–element bondsvs.stable terminal Sb–H bonds

“…Both compounds revealed a see-saw structure typical of similar pincer-ligand stabilized pnictogen cations. 7 c ,21 The triflate anion is only weakly coordinated to the central atom in 2-Bi ( cf. Bi(1)⋯O(1) 3.010(4) Å), while no Sb(1)⋯O contact is found in 4-Sb .…”

Exploring the Role of Strong Intramolecular Coordination of the 2‐(2'‐pyridyl)phenyl Group in Heavy Main Group Halides: Insights from Synthesis, Structural, and Bonding Analyses

“…[BAr 4 ] – [where Mes = 2,4,6‐Me 3 C 6 H 2 , Ar = 3,5‐(CF 3 ) 2 C 6 H 3 ] using sterically bulky meta ‐terphenyl substituents. [8c] The significance of compound 4 also stems from the fact that this is the second example of a monoorganobismuth(III) trichloride anion and first one to contain an intramolecularly coordinating substituent. The corresponding first example was reported by Norman and co‐workers as a pyridine adduct of arylbismuth chloride, namely [4‐ t BupyH] [Ph(4‐ t Bupy)BiCl 3 ] (4‐ t Bupy= 4‐ tert ‐butylpyridine) …”

“…[16a] This distance matches well with the values observed in related monoorganobismuth(III) chloride with N containing pendant arm(s), such as, Bi[C 6 H 3 ‐2,6‐(CH=N‐ t Bu) 2 ]Cl 2 [2.470(7) Å, 2.499(6) Å],[2d] Bi[C 6 H 3 ‐2,6‐(CH=N‐2',6'‐Me 2 C 6 H 3 ) 2 ]Cl 2 [2.500(4) Å, 2.522(4) Å],[2d] Bi[2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 ]Cl 2 [2.561(3) Å, 2.570(4) Å],[3a] Bi[2,6‐{MeN(CH 2 CH 2 ) 2 NCH 2 } 2 C 6 H 3 ]Cl 2 [2.583(5) Å],[3b] {Bi[C 6 H 3 ‐(2,6‐CH=N‐2',6'‐Me 2 C 6 H 3 ) 2 ]Cl}[CB 11 H 12 ] [2.465(3), 2.498(2) Å]. [8a] The Bi2–Cl1 bond length trans to the pyridyl N‐atom is 2.715(5) Å, while the Bi2–Cl2 and Bi2–Cl3 bond lengths are 2.696(4) Å and 2.744(4) Å respectively. All these Bi–Cl bond lengths and their associated bond angles are in good agreement with those observed in the reported monoorganobismuth(III) trichloride anion, namely [BiCl 3 Ph(4‐ t Bupy)] – .…”

“…This observation was further corroborated by Density Functional Theory (DFT) calculations, which suggested that the stability of both monomeric organotellurinic(IV) acid and non‐NHC carbenoid derivatives relies on the σ‐hole participation of the element center with the strong intramolecular coordination ability of the pyridyl N‐atom of the ppy group. It is worth mentioning that the Bi analogues of non‐NHC derivatives, namely bismuthenium cation or halo bismuthenium cations have gained significant attention with respect to their synthesis and interesting structural features . The extraordinary intramolecular stabilization effect offered by the N atom of the ppy group prompted us to probe its utility towards the isolation of monomeric heavy main group monoorgano halides.…”