Advanced preparation of functionalized triarylbismuths and triheteroaryl-bismuths: new scope and alternatives

How Changing the Bridgehead Can Affect the Properties of Tripodal Ligands

“…Our attempts to obtain the unsubstituted ligands E(2‐py) 3 (E=As, Sb, Bi) using the in situ reaction of 2‐lithiopyridine with ECl 3 were only successful for E=As, apparently as a result of reductive elimination of bipyridine from E(2‐py) 3 and the generation of elemental Sb or Bi for the heavier Group 15 elements. This is in line with a previous report which showed that the ligand Bi(2‐py) 3 could not be obtained even from the reaction of BiCl 3 with the more stable 2‐(ZnBr)‐pyridine reagent . A very recent study also failed to isolate the tris‐pyrazolato bridged bismuth ligand .…”

“…[8][9][10] Our focus in this area has been the exploration of the reactivity and coordination chemistry of Group 13 and 14 tris-2-pyridyl ligands in which metallic or semi-metallic elements are present (like the aluminate shown in Figure 1c). [26] Avery recent study also failed to isolate the tris-pyrazolato bridged bismuth ligand. Our attempts to obtain the unsubstituted ligands E(2-py) 3 (E = As,S b, Bi)u sing the in situ reaction of 2-lithiopyridine with ECl 3 were only successful for E = As, [25] apparently as ar esult of reductive elimination of bipyridine from E(2-py) 3 and the generation of elemental Sb or Bi for the heavier Group 15 elements.T his is in line with ap revious report which showed that the ligand Bi(2-py) 3 could not be obtained even from the reaction of BiCl 3 with the more stable 2-(ZnBr)-pyridine reagent.…”

One-Pot Synthesis of Hypervalent Diaryl(iodo)bismuthanes from o-Carbonyl Iodoarenes by Zincation

“…Several mild bismuth-carbon bond forming reactions have been reported, which include the treatment of aryl iodides with bismuth shot in the presence of Cu and CuI by ball milling [17], the arylation of bismuth(III) carboxylates by sodium tetraarylborate [18], and the reaction of BiCl 3 with organozinc reagents [19]. To achieve wide functional group tolerance, we chose organozinc reagents because they are compatible with carbonyl functionalities such as ester, acetyl, and even formyl substituents, and the chemistry of these reagents is well established [20][21][22].…”

Palladium‐Catalyzed Cross‐Coupling Reaction of Functionalized Aryl‐ and Hetero­arylbismuthanes with 2‐Halo(or 2‐Triflyl)­azines and ‐diazines

“…[15] These organometallic reagents can be easily prepared, [16] chromatographed, and stored in air at room temperature. In addition, their low toxicity makes them extremely attractive species for methodology development.…”