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

Cationic Crown Ether Complexes of Germanium(II)

“…For example, In + readily fits into the cavity of [18]crown-6 but forms a crown ether sandwich with two molecules of [15]crown-5. [12][13][14] We now report that crown ethers can also support germanium cations and allow facile access to a series of unprecedented mono-and dicationic Ge II complexes. We have examined three differently sized crown ethers, [12]crown-4, [15]crown-5, and [18]crown-6, [20] which all form complexes with cationic germanium(II), each with unique structural characteristics.…”

“…Coordination complexes with every type of metal ion in the periodic table have been described. [9] In the p block, reported examples of crown ether complexes with metallic cations include aluminum, [10] gallium, [11] indium, [11][12][13][14] thallium, [15] tin, [16] lead, [9] and bismuth. [9] Neutral crown ether complexes of nonmetals are also known, although the nonmetal atom is usually situated outside the cavity of the macrocycle.…”

Crown ether complexes of tin(II) trifluoromethanesulfonate

“…Recently, we found that differently-sized crown ethers allow for the ready isolation of Ge II cations, including dications that do not feature any covalent bonds to the semi-metal center; [3][4][5] these results complement the observations of systems with the related cryptand ligands [6] and suggest that the use of such macrocyclic ligands should provide for a rich and interesting chemistry for even more of the p-block elements. In fact, we had previously found that crown ether ligation of our indium(I) trifluoromethanesulfonate (triflate) reagent In I O 3 SCF 3 (In I OTf) [7] allows for the isolation of stable and isolable monomeric indium(I) complexes that exhibit unusual and perhaps useful modes of reactivity including oxidative addition into aliphatic carbon-chlorine bonds [8][9][10][11].…”

Synthesis and structure of an indium(I) “crown sandwich”

“…In contrast to most other donors, the ligation of the In I center by the crown ethers occurs without any evidence of disproportionation [31,32] and it also changes the reactivity of the In(I) reagent dramatically [30]. In this note, we present the results of some of our investigations concerning the ligation of InOTf with the smaller crown ether 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5) that results in the formation of a new, and potentially more reactive, In I reagent.…”

“…In our laboratory, we have discovered two routes to the unusually soluble indium(I) trifluoromethanesulfonate salt (indium(I) triflate, InOS-O 2 CF 3 , InOTf, 1); the most effective synthesis of 1 involves the protonolysis of Cp*H from the organometallic precursor Cp * In [26]. As summarized in Scheme 2, this In I reagent has already exhibited interesting and sometimes unique chemistry, including the formation of new In-carbon and In-element bonds [24,[27][28][29][30].…”