An Improved Synthesis and Isolation of Tribenzylbismuth

Synthesis and Structure of Bis- and Tris-Benzyl Bismuth Complexes

“…The structure and bonding motif of bismuth benzyl compounds was further explored with the synthesis of Bi(CH 2 Ph) 3 , 2 . , A single set of benzyl resonances was observed by 1 H NMR spectroscopy in benzene, which is consistent with that observed in compound 1 . Single crystals suitable for X-ray crystallography were grown from a concentrated hexane solution at −30 °C, Figure .…”

“…The stability of the homoleptic bismuth allyl complexes, namely tris(allyl)bismuth and tris(methylallyl)bismuth, is quite limited, with the compounds being temperature, light, air, and vacuum sensitive . In contrast, earlier studies have shown that although Bi(CH 2 Ph) 3 is air sensitive, it has a melting point of 65 °C and begins to decompose thermally at 110 °C . Compound 1 shows no evidence of decomposition from prolonged exposure to light or vacuum.…”

“…Surprisingly, examination of the literature showed that the tris(benzyl) complex, Bi(CH 2 Ph) 3 , , originally reported in 1957 had never been crystallographically characterized. This is the only example of a bismuth-benzyl compound in the literature, despite the fact that benzyl is a special type of alkyl group that can coordinate in a variety of ways to metals, Scheme . − To determine how bismuth benzyl complexes compared structurally to BiPh 3 and Bi(allyl) 3 complexes, the reactions of a benzyl Grignard reagent with bismuth chlorides were explored.…”

“…This is the only example of a bismuth-benzyl compound in the literature, despite the fact that benzyl is a special type of alkyl group that can coordinate in a variety of ways to metals, Scheme . − To determine how bismuth benzyl complexes compared structurally to BiPh 3 and Bi(allyl) 3 complexes, the reactions of a benzyl Grignard reagent with bismuth chlorides were explored. The reaction with the NCN pincer aryl ligated complex, Ar′BiCl 2 [Ar′ = 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ], was studied first because this ancillary Ar′ ligand has proven useful in isolating many new types of complexes. − The homoleptic complex, Bi(CH 2 Ph) 3 , , was synthesized for crystallographic studies and the results are reported here.…”

Dispersion interaction of the type-bismuth···π arene in substituted bismuthines

“…Bi(CH 2 C 6 H 4 -X-2) 3 (X = H, Cl, Br), starting from the corresponding organomagnesium reagent and BiCl 3 , but only the melting points and elemental analyses were reported. 6 Later on Remington et al published the spectroscopic characterization of Bi(CH 2 C 6 H 5 ) 3 ( 1 H and 13 C NMR, IR), 7 while its crystallographic characterisation was reported only recently by Evans and coworkers. 8 In an experimental and theoretical study in 2009 the first crystal structure of a trisbenzyl bismuth derivative, [Bi(CH 2 C 6 H 4 -Cl-2) 3 ] 2 , was reported.…”