On the reactions of the tetraindiumcluster In4[C(SiMe3)3]4 with phenylselenium and phenyltellurium bromides

On the reactions of the tetraindium cluster In4[C(SiMe3)3]4: Insertion of the monomeric fragments InC(SiMe3)3 into chalcogen–chalcogen bonds

“…Å in 2, 3 and 5, respectively, while expectedly the bond lengths to the bridging chalcogen atoms are lengthened to 2.594, 2.744 and 2.929 Å on average. These values correspond well to those reported previously [10][11][12][13][14][15][16][17][18][35][36][37][38][39][40]. All bridging chalcogen atoms adopt a trigonal pyramidal coordination sphere.…”

“…In contrast to the cyclopentadienyl compounds it exhibits strong In-In bonding interactions and has an almost undistorted tetrahedral cluster of four indium atoms in an oxidation state of +I [8,9]. Compound 1 is soluble in hydrocarbons and is applicable as a facile source of monomeric InR fragments [R = C(SiMe 3 ) 3 ] in a number of unprecedented and remarkable chemical reactions [10][11][12][13][14][15][16][17][18]. For instance, novel indium(III) chalcogenides were obtained through the complete oxidation of the cluster atoms by elemental chalcogens or suitable chalcogen atom donors to give heterocubane-type molecules In 4 R 4 E 4 (E = O, S, Se, Te) [8,[19][20][21].…”

“…For instance, novel indium(III) chalcogenides were obtained through the complete oxidation of the cluster atoms by elemental chalcogens or suitable chalcogen atom donors to give heterocubane-type molecules In 4 R 4 E 4 (E = O, S, Se, Te) [8,[19][20][21]. Reactions with phenylchalcogen bromides, H 5 C 6 -E-Br (E = Se, Te), afforded the dimeric chalcogenolates [PhE(R)InBr] 2 (E = Se, Te) [10]. Indium(III) chalcogenolates obtained from indium monohalides and diphenyl dichalcogenides [22] have been extensively applied in organic synthesis to generate carbon-chalcogen bonds.…”

Te–Te and Te–C bond cleavage reactions using a monovalent gallanediyl

“…43 Reactions of trivalent group 13 compounds (MR 3 , MH 3 ; M = Al, Ga, In) with elemental chalcogens E or chalcogen sources such as R 3 PvE (E = O, S, Se, Te) typically occur with insertion of the chalcogen atom into the M-C/H bond and subsequent formation of dimeric ([R 2 M-μ-ER] 2 ) or tetrameric ([RME] 4 ) compounds, whereas divalent (R 4 M 2 ) as well as monovalent group 13 compounds RM (M = Al, Ga, In, Tl) react with insertion of the chalcogen atom into the M-M bond. [44][45][46][47][48][49] In addition, E-Br bond cleavage reactions of PhEBr (E = Se, Te) upon treatment with the monovalent In(I) cluster [(Me 3 Si) 3 C] 4 In 4 50 as well as of Te-Te bond cleavage reactions of Ph 2 Te 2 by reaction with Ga(I) 26 and In(I) compounds 51 as well as with base-stabilized GaH 3 30 were reported. However, to the best of our knowledge, the cleavage of the Te-C bond of diorganyltellanes upon reaction with monovalent group 13 compounds RM has never been observed before.…”

Small Inorganic Rings in the 21st Century: From Fleeting Intermediates to Novel Isolable Entities

“…The (449), respectively. 291 In 4 [C-(SiMe 3 ) 3 ] 4 also reacts with diaryl dichalcogenides REER (E = S, Se, and Te; R = Ph or tolyl) to yield the corresponding In 2 E 2 rings [(Me 3 Si) 3 CIn(ER)(μ-ER)] 2 (450−452; Figure 21). 292 The thermally stable group 13 dimetallenes Dipp ArMMAr Dipp (M = Ga and In) combine with elemental sulfur to give the centrosymmetric dimers [ Dipp ArGa(μ-S)] 2 (453) and [ Dipp ArIn-(μ-S)] 2 (454), respectively.…”