Synthesis and Characterization of R₂BiCl and RBiCl₂ [R = CH(SiMe₃)₂]

Abstract

Reaction of RLi [R = CH(SiMe3)2] with BiCl3 in a 2:1 ratio gives R2BiCl (1). RBiPh2 is formed by the action of RMgCl on Ph2BiCl. Reaction of RBiPh2 with HCl in CHCl3 gives RBiCl2 (2), which crystallizes from diethyl ether as the solvate 2·0.5Et2O. The crystal structures of 1 and 2·0.5Et2O have been determined by X-ray diffraction. Crystals of 1 consist of pyramidal R2BiCl molecules, whereas in crystals of 2·0.5Et2O there are {[RBi(Cl)Cl]2·Et2O}x chains with chloro bridges. The diethyl ether molecules are weakly associated to neighboring bismuth atoms in the chain.

Synthetic and Structural Studies of Lead and Bismuth Organohalides Bearing a β‐Diketiminato Ligand

“…2). By comparing the BiϪCl bond lengths (2.675(1) and 2.736(1) Å ) in 4 they were found shorter than similar BiϪCl linkages observed in Ar 2 BiCl (2.483(9) Å ), [16] [(Me 3 Si) 2 CH] 2 BiCl (2.530(2) Å ) [27], in ArBiCl 2 (2.539(1) and 2.501(1) Å ), and [ArBiCl 2 ] 2 (2.496(6) to 2.544(5) Å ) (Ar ϭ 2,6-Mes 2 C 6 H 3 ; Mes ϭ 2,4,6-Me 3 C 6 H 2 ) [28] however, they show good agreement with that found for Ar 2 BiCl (Ar ϭ 2-(Me 2 NCH 2 )C 6 H 4 (C 9 H 12 N) (2.667(2) Å ) [15]. Compound 4 displays shorter and longer BiϪN bond lengths in the range from 2.232(2) to 2.842(3) Å .…”

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]

“…Recent developments show that these difficulties can be overcome at least partially by two strategies. One is the use of bulky substituents such as (Me 3 Si) 2 CH [9][10][11][12][13][14], 2,6-R 2 C 6 H 3 (R = Mes [15][16][17][18][19], 2,6-i Pr 2 C 6 H 3 [18]), 2,4,6-R 3 C 6 H 2 [(Me 3 Si) 2 CH [20][21], Ph [22,23]], 2,6-[(Me 3 Si) 2 CH] 2 -4-(Me 3 Si) 3 C-C 6 H 2 [24][25][26][27], 2,6-Mes 2 -4-t Bu-C 6 H 2 [19]. Another strategy is to use one pendant arm ligands such as 2-(MeOCR 2 )C 6 H 4 (R = Me [28][29][30], CF 3 [31]) and 2-(Me 2 NCH 2 )C 6 H 4 [32], or ''pincer" ligands like 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 [32,33], 2,6-[MeN(CH 2 CH 2 ) 2 NCH 2 ] 2 C 6 H 3 [33], and 2,6-(ROCH 2 ) 2 C 6 H 3 (R = Me [34], t Bu [34,35]).…”

[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 is the use of bulky substituents, which afford isolation of monomeric monohalide species, e.g. [2,4,6‐(CF 3 ) 3 C 6 H 2 ] 2 BiCl 11, [(Me 3 Si) 2 CH] 2 BiCl 12, or [2,6‐Mes 2 C 6 H 3 ] 2 BiCl 13. Even with such bulky ligands the dihalides usually form at least dimers, e.g.…”