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

Abstract

The first crystallographic characterization of bismuth complexes containing benzyl ligands is reported. The NCN pincer ligand complex, Ar′BiCl 2 [Ar′ = 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ], reacts with (PhCH 2 )MgCl to form Ar′Bi(η 1 -CH 2 Ph) 2 in high yield. X-ray crystallography and spectroscopic studies confirm η 1 -bonding of the benzyl ligands in Ar′Bi(η 1 -CH 2 Ph) 2 as well as in the homoleptic Bi(η 1 -CH 2 Ph) 3 .

Understanding the Origin of Phosphorescence in Bismoles: A Synthetic and Computational Study

“…1 H NMR (500 MHz, C 6 D 6 ): δ 6.92 (s, 2H, ArH), 2.75 (dq, 2 J HH = 15.1 Hz, 3 J HH = 7.6 Hz, 2H, CH 2 CH 3 ), 2.66 (dq, 2 J HH = 15.0 Hz, 3 J HH = 7.5 Hz, 2H, CH 2 CH 3 ), 2.50 (s, 6H, CH 3 in Mes), 2.12−2.23 (m, 4H, CH 2 CH 3 ), 2.10 (s, 3H, CH 3 in Mes), 1.06 (overlapping t, 3 J HH = 7.5 Hz, 12H, CH 2 CH 3 ). 13 C{ 1 H} NMR (126 MHz, C 6 D 6 ): δ 161.3 (ArC), 147.8 (ArC), 137.5 (ArC), 129.1 (ArC), 30.8 (CH 2 ), 28.1 (CH 3 in Mes), 26.5 (CH 2 ), 21.1 (CH 3 in Mes), 19.4 (CH 3 ), 14.5 (CH 3 ). Anal.…”

Organic Compounds of Bismuth: Synthesis, Structure, and Applications

“…Triorganyl derivatives of bismuth R 3 Bi are synthesized, as a rule, from organomagnesium or organolithium compounds in high yields. For example, the benzyl derivatives of bismuth were synthesized by the reaction of arylbismuth dichloride Ar'BiCl 2 (Ar' = 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ) with benzylmagnesium chloride in tetrahydrofuran (THF) giving Ar'Bi(η 1 -CH 2 Ph) 2 in high yields (Scheme 1) [3]. Tribenzylbismuth Bi(η 1 -CH 2 Ph) 3 was synthesized similarly.…”

“…The (iPr 2 P−Ace) 3 Bi and (iPr 2 P−Ace) 2 BiPh derivatives (Ace is acenaphthene-5,6-diyl) were synthesized from bismuth chloride and aryllithium [15] via the following scheme (Scheme 12). The synthesis of the neutral Bi-containing tris-2pyridyl ligand (6-Me-2-Py) 3 Bi, which transforms into the copper complex {[(6-Me-2-Py) 3 Bi]Cu-(MeCN)} + [PF 6 ] − upon the treatment with [Cu(MeCN) 4 ] + [PF 6 ] − in an acetonitrile solution (Scheme 13), was described in [16].…”

“…3 linked with each other by two bridging organosulfonate ligands through the oxygen atoms. The coordination mode of the bismuth atoms is octahedral, one position is occupied by a lone electron pair, and the Bi−C and Bi−O bond lengths are 2.226(7), 2.221(10) Å and 2.361(4)−2.384(7) Å, respectively.…”

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

“…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. The latter shows the presence of intermolecular dispersion interactions of the type Bi•••π arene between two neighboring molecules, which provides dimers, and as a result of these Bi•••π interactions and π•••π stacking a 2D network is formed.…”