Millimeter wave rotational spectra of indium monofluoride

Abstract

Abstract. The millimeter wave rotational spectra of indium monofluoride (InF) have been studied in the 250-300 GHz frequency region. Three rotational transitions of 115InF in the v=0, 1 and 2 vibrational states and two rotational transitions of the less abundant mlnF in the v = 0 state with resolved hyperfine structures have been measured. The analysis including previous measurements on the lower rotational transitions in the microwave region yielded improved and extended sets of Dunham parameters. The comparison of the results for the two isotopic species of InF indicates a similar deviation from the Born-Oppenheimer approximation as for InCl.

Development of the Chemistry of Indium in Formal Oxidation States Lower than +3

“…Some compounds, such as InCl, InBr, InI, or (η 5 -C 5 R 5 )In (R = H or Me), vaporize on heating without decomposition or disproportionation; at sufficiently high temperatures, the entropy advantage drives even robust In III molecules such as In 2 O 3 and InCl 3 to decompose, at least partially, to the corresponding In I compound and elemental nonmetal. Other In I compounds, such as InH, InF, InCN, or InNC, require high-energy reactions for their formation. − For example, InH is generated by the reaction of the molten metal with H 2 at 1000−1200 °C prior to characterization by its high-resolution IR spectrum measured either in emission or in absorption. , In a similar vein, InF is formed by heating together the metal and InF 3 , while the reaction of laser-ablated In vapor with [CN] 2 or CH 3 CN in an Ar carrier gas affords the two isomers InCN and InNC, whose structures and vibrational/rotational properties have been fixed by their microwave spectra . The electron diffraction patterns of the derivatives CpIn, where Cp = C 5 H 5 , C 5 H 4 Me, and C 5 Me 5 , serve to confirm the η 5 -coordination of the cyclopentadienyl ring.…”

“…Otherwise the necessary steric bulk is provided by multidentate ligands. Some of the best known organoindium(I) compounds are the cyclopentadienyl derivatives, ,,− but even here the “bite” of the pentahapto ligand is generally insufficient to prevent aggregation in the crystalline state. Whereas the pentamethylcyclopentadienyl compound is a loosely bound hexamer, however, increasing the bulk of the ligand by substituting Ph 2 P for one of the CH 3 groups does favor a monomeric molecular crystal structure in which the metal atom is simply η 5 -coordinated to the cyclopentadienyl ring .…”

“…Other In I compounds, such as InH, InF, InCN, or InNC, require high-energy reactions for their formation. [141][142][143][144][145][146][147][148][149][150][151][152][153] For example, InH is generated by the reaction of the molten metal with H 2 at 1000-1200 °C prior to characterization by its high-resolution IR spectrum measured either in emission or in absorption. 81,141 In a similar vein, InF is formed by heating together the metal and InF 3 , 144 while the reaction of laser-ablated In vapor with [CN] 2 or CH 3 CN in an Ar carrier gas affords the two isomers InCN and InNC, whose structures and vibrational/rotational properties have been fixed by their microwave spectra.…”

Indium(I) Hexafluoropnictates (InPnF6; Pn = P, As, Sb)

“…A good measure of the strength of their Lewis acidity is the reaction enthalpy ∆H(MF x + F -= [MF x+1 ] -), i. e. fluoride ion affinity (FIA). [9] The main driving forces for the formation of InPnF 6 compounds [Equation (1)] are the difference in fluoride ion affinities (FIA) of BF 3 (347.7 kJ mol -1 ) [9] and PnF 5 (Pn = P: 397.1 kJ mol -1 ; As = 443.1 kJ mol -1 ; Sb = 503.3 kJ mol -1 ) [9] and the lattice energy differences between the starting InBF 4 (2). [10,11] …”

“…[2] Unstable InF has only been observed in the gas phase. [2][3][4][5] Furthermore, reports of complex fluorides with In + in a solely fluorine environment are also scarce. [6,7] One rare example is InBF 4 , which has been prepared by reaction of elemental In with BF 3 in anhydrous hydrogen fluoride (aHF).…”