Reactivity of N,C,N-Chelated Antimony(III) and Bismuth(III) Chlorides with Lithium Reagents: Addition vs Substitution

Abstract

N,C,N-chelated antimony(III) and bismuth(III) chlorides L 1,2 MCl 2 (1−4: for L 1 , M = Sb (1), Bi (3); for L 2 , M = Sb (2), Bi (4)) containing ligands L 1,2 (wherewere prepared by reactions of lithium precursors with SbCl 3 or BiCl 3 . The identities of 1−4 were established both in solution ( 1 H and 13 C NMR spectroscopy) and, in the case of 1−3, in the solid state using single-crystal X-ray diffraction analysis. Treatment of antimony derivatives 1 and 2 with 2 molar equiv of R′Li (R = Me, n-Bu, Ph) yielded the set of substituted 1,3-(R′) 2 -2-R-7-(CHNR)-1H-2,1-benzazastiboles 5−10 (where R = t-Bu, 2,6-Me 2 C 6 H 3 and R′ = Me, n-Bu, Ph) as a result of a nucleophilic attack of one of the lithium compounds across the imino CN functionality. In contrast, analogous reactions between bismuth congeners 2 and 4 and R′Li (2 equiv, R′ = Me, Ph) gave L 1,2 BiR′ 2 (11−13: for L 1 , R′ = Me (11), Ph (12); for L 2 , R′ = Me ( 13)) as products of substitution of chlorine atoms. Compounds 5−13 were characterized by the help of 1 H and 13 C NMR spectroscopy. The molecular structures of 8, 9, and 13 were unambiguously established using single-crystal X-ray diffraction analysis.

From Dibismuthenes to Three‐ and Two‐Coordinated Bismuthinidenes by Fine Ligand Tuning: Evidence for Aromatic BiC3N Rings through a Combined Experimental and Theoretical Study

“…The starting N,C,N‐chelated bismuth chlorides [C 6 H 3 ‐2,6‐(CHNR) 2 ]BiCl 2 [where R= t Bu ( 1 ) or 2′,6′‐Me 2 C 6 H 3 ( 2 )] were prepared according to the literature procedure22a and their congener [C 6 H 3 ‐2,6‐(CHN‐4′‐Me 2 NC 6 H 4 ) 2 ]BiCl 2 ( 3 ) was obtained by an analogous procedure in 56 % yield. Using an analogous synthetic protocol, N,C‐chelated bismuth compounds [C 6 H 2 ‐2‐(CHN‐2′,6′‐ i Pr 2 C 6 H 3 )‐4,6‐( t Bu) 2 ]BiCl 2 ( 4 ) and [C 6 H 2 ‐2‐(CH 2 NEt 2 )‐4,6‐( t Bu) 2 ]BiCl 2 ( 5 ) were easily accessible in 66 and 58 % yields, respectively.…”

“…The molecular structure of 3 [as a chloroform solvate, 3⋅ (CHCl 3 ) 3 ] closely resembles that of its analogue, 1 22a. The central bismuth atom is strongly coordinated by the NCN donor set of the respective pincer ligand [cf.…”

“…The central bismuth atom is strongly coordinated by the NCN donor set of the respective pincer ligand [cf. BiN distances: 2.500(4) and 2.522(4) Å in 3 , 2.470(7) and 2.499(6) Å in 1 22a] in a pseudo‐meridional fashion [cf. N‐Bi‐N bonding angles: 142.82(12)° in 3 , 142.89(18)° in 1 22a].…”

Synthesis and structure of 6-diphenylphosphinoacenaphth-5-yl bismuth compounds

“…1 Alternatively, the donor ligands may also bind to transition metal ions giving rise to interesting complexes that involve metal bismuth interactions. The vast majority of these ligands possess Ndonors, [2][3][4][5][6][7][8] whereas as P-donors are only occasionally encountered. [9][10][11][12][13][14][15] As part of our research programme on peri-substituted scaffolds, we recently prepared the monoarylbismuth dichloride RBiCl 2 (1a, R = 6-diphenylphosphinoacenaphth-5-yl), the analogous arylantimony dichloride RSbCl 2 (1b) 16 as well as the diarylantimony chloride R 2 SbCl (2b) and the triarylantimony R 3 Sb (3b).…”

Organic Compounds of Bismuth: Synthesis, Structure, and Applications

“…25) in which two bismuth atoms are linked to each other by bridging oxygen-containing ligands, such as O{(CH 2 ) 2 BiPh 2 } 2 , MeN(CH 2 −2-C 6 H 4 BiR 2 ) 2 , and S(CH 2 −2-C 6 H 4 BiR 2 ) 2 (R = Me, Ph), were synthesized and characterized by XRD[32].Hypervalent interactions between the O or S atoms and bismuth atoms are observed in the structures of O{(CH 2 ) 2 BiPh 2 } 2 and S(CH 2 −2-C 6 H 4 Bi-Ph 2 ) 2 (Bi⋅⋅⋅O 3.203(3), 3.126(3) Å at the sum of the van der Waals radii of bismuth and oxygen equal to 3.52 Å and Bi⋅⋅⋅S 3.3254(12),3.3013…”