Structure and reactivity of derivatives of dihalogenomethyl indium(III) halides, X2InCHX2 (X=Cl, Br, I)

The insertion reactions of “crowned” indium(I) trifluoromethanesulfonate into carbon–chlorine bonds

“…elemental halogens; the Ch-Ch bonds in some peroxy-acids (Ch = O), organo-dithiolates (Ch = S), or organo-diselenides (Ch = Se); and certain other reactive heteronuclear bonds [10]. Of particular import to the work presented herein is the reported insertion of In I halides into dihalomethanes (CH 2 X 2 ; X = Br, I) to yield In III compounds of the type X 2 InCH 2 X [17,18] or into haloforms (CHX 3 ; X = Cl, Br, I) to provide In III compounds of the form X 2 InCHX 2 [19,20]. These products were generally isolated as Lewis base adducts or as phosphonium ylides.…”

Crown Ether Ligation: An Approach to Low‐Oxidation‐State Indium Compounds

“…For example, the smaller In III ion is offset from the center of the O 6 ring to allow for four shorter InÀO contacts (2.517(5) to 2.550(5) ) and thus leaves two much longer In···O contacts (2.738(5) and 2.756(5) ). The InÀCl bond length of 2.304(2) is one of the shortest such distances so far reported; [24] however, the In À C bond length of 2.174 (7) is typical of such bonds [25,26] reported in the Cambridge Structural Database (CSD). [27] The minor deviation of the Cl-In-C angle from linearity (171.82 (19)8) is consistent with the asymmetric ligation of the In center by the crown ether.…”

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

“…Similarly, oxidative insertions of InX into the carbon-halogen bonds of organyl dihalides, RR 1 CX 2 (R = R 1 = H, X = Br, I [3,4]; R = H, R 1 = CN, X = Br [5]; R = H, R 1 = PhCO, X = Cl [6,7]) and trihalides, RCX 3 (R = H, X = Cl, Br, I [8][9][10]; R = CN, X = Cl [11]) lead to the corresponding halogenoalkyl, X 2 InC-RR 1 X and the dihalogenoalkyl, X 2 InCRX 2 compounds of indium(III). 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.…”

“…Similarly, oxidative insertions of InX into the carbon-halogen bonds of organyl dihalides, RR 1 CX 2 (R = R 1 = H, X = Br, I [3,4]; R = H, R 1 = CN, X = Br [5]; R = H, R 1 = PhCO, X = Cl [6,7]) and trihalides, RCX 3 (R = H, X = Cl, Br, I [8][9][10]; R = CN, X = Cl [11]) lead to the corresponding halogenoalkyl, X 2 InC-RR 1 X and the dihalogenoalkyl, X 2 InCRX 2 compounds of indium(III). 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].…”