Synthesis and molecular structures of dialkylselenonium methylide complexes of indium tribromide

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

“…As a result, a strong folding across the In-In axes of the molecules was detected (40.2°and 35.7°, respectively). The In-Se (270.2 pm on average), the In-Te (288.8 pm) and the InBr distances (250.5 pm) are in the ranges characteristic of the respective bonding situation with tricoordinated chalcogen [14][15][16] or terminal bromine atoms [16,17]. Owing to the considerable puckering of the heterocycles all angles of the rings are smaller than 90°(2: In-Se-In 89.3°; Se-InSe 83.9°; 3: In-Te-In 86.8°; Te-In-Te 87.5°).…”

Dihalogen–halogenomethyl complexes of indium(III) X2InCH2X (X=Br, I): Simultaneous coordination of soft and hard ligands

“…The averaged indium-halogen and indium-carbon distances for compounds 1-5 are close to other ylide complexes of InBr 3 of general structure Br 3 InCH 2 L (L = Et 3 N, Ph 3 P, Ph 3 As, Ph 3 Sb, Bn 2 S) [13][14][15][16][17]. On the other hand, compounds 4 and 5 show abnormal longer indium-oxygen bond distances when compared with the values of 2.20(1), 2.14(1) and 2.281(6) Å A 0 measured in the fac octahedral InX 3 (dmso) 3 (X = Cl, Br) [29], in the ionic [InCl 2 (Ph 3 PO) 4 ] [InCl 4 ] [29] and in the closely related Br 2 In(Ph 3 PO) 2 CH 2 Br [16] compounds, respectively.…”

“…NMR spectroscopy unequivocally revealed the sulfonium methylide ligands attached to the indium(III) centers according to the singlets corresponding to the methylide groups observed from 2.60 to 2.86 ppm, which are in the typical range observed for other indium(III) ylides [13][14][15][16][17].…”

“…While some of these compounds contain nucleophilic alkyl substituents capable of coupling to electrophiles [5][6][7]10,11], the methylene dihalide derivatives have been used mainly as models for coordination chemistry studies. Independently, we have determined that ligands with the hard donor atom oxygen, L H , such as ethers, dimethylsulfoxide and triphenylphosphine oxide coordinate to the metallic center of the Br 2 In(L H ) n CH 2 Br complex [12], while bases with soft donor atoms, L S , displace the bromine atom of the bromomethyl substituent to form corresponding ylides of InBr 3 of general structure Br 3 InCH 2 L S [13][14][15][16][17].…”

Selenium-Directed ortho-C–H Borylation by Iridium Catalysis

“…Compounds 1b – 1s were prepared according to a reported procedure . Compound 1w was prepared according to a reported procedure …”