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Organometallic Compounds with Homonuclear Bonds between Bismuth Atoms, 70 Years after Paneth' Report on the Violet Dimethyl Bismuth Compound

“…Only with group 13 element acceptors the coordination of a dibismuthane through the lone pair of bismuth has been achieved [29]. With Fe 2 (CO) 9 insertion of the Fe(CO) 4 group into the Bi-Bi bond of a dibismuthane is observed [37]. Also the reaction of Co 2 (CO) 8 with Ph 4 Bi 2 leads to a transfer of the diorgano bismuth moiety [38].…”

“…Bulky silyl and stannyl substituents, R ϭ (Me 3 C) 3 Si, (Me 3 Si) 3 Si, (Me 3 Si) 3 Sn were used by Linti et al for the stabilisation of bismuth rings [9,45]. The rings form in reactions between BiBr 3 and silyl or stannyl alkali metal reagents which serve not only as source for the substituents at Bi but also as reducing agents.…”

“…The first organobismuth(I) compounds, the dibismuthene RBiϭBiR, R ϭ 2,4,6-[(Me 3 Si) 2 CH] 3 C 6 H 2 [7] and the cyclobismuthanes (RBi) n (n ϭ 3, 4; R ϭ (Me 3 Si) 2 CH [8]) were reported in 1997 and 1998, respectively. Recently also a bicyclic compound, R 5 Bi 8 (R ϭ (Me 3 Si) 3 Sn [9]) was described. Presently known types of organometallic compounds with Bi-Bi bonds and RBi are shown in Figure 1.…”

Reduction vs. Metathesis in the Reactions of Bismuth Tribromide with a Bulky Lithium Silanide – An Experimental and Theoretical Study

“…Only seventeen examples of such species, whose structures have been determined by X-ray diffraction, are well-known up to now. Primarily, these are homonuclear [1][2][3] (four examples) and heteronuclear [1,3,[5][6][7][8][9][10][11] complexes (thirteen examples) containing silyl groups of various steric requirements [SiMe 3 , SitBu 3 , Si(SiMe 3 ) 3 ], which play a stabilizing role here. In these compounds, bismuth displays the oxidation states +1, +2 and +3.…”

Synthesis and Structures of Polyhedral Hexa‐ and Octagallium Cluster Compounds

“…Here, at least one gallium atom bears no substituent and the gallium cores can be derived from gallium element structures. Polyhedral cluster compounds (Scheme 1) include Ga 4 (R x ) 4 10 (R x = R 1 , [11] R 2 , [12] R 3 , [7b] C(SiMe 3 ) 3 , [13] tmp, [14] N(SiMe 3 )dipp) [14] ), trigonal bipyramidal Ga 4 Si core cluster [(Me 3 SiSi){Ga(R 1 )} 3 (GaSiMe 3 )] -11, [15] distorted octahedral Ga 6 R 4 6 [R 4 = SiMe(SiMe 3 ) 2 ] 12, [16] closo-[Ga 6 {Si(CMe 3 ) 3 } 4 -(CH 2 Ph) 2 ] 2-13 [16] and closo-[Ga 6 Mes 4 (L) 2 ] (L = C{iPrNC(Me)} 2 ) 14, [17] square antiprismatic [Ga 8 (fluorenyl) 8 ] 2-15 [18] and capped-trigonal prismatic [Ga 9 tBu 9 ] 0,1-16. [19] Other Ga 6 compounds show structures, which are not polyhedral.[Ga 6 (SiPh 2 Me) 8 ] 2has a planar Ga 6 -core [20] and GaCp* forms a hexamer in solid state, [21] where no Ga-Ga bonding interactions are on work, but the hexamer is stabilized by CH/HC dispersive interactions.…”