Electronic and molecular structure of pentafluorooxotellurate(1-)

Miller, P. K.; Abney, Kent D.; Rappé, Anthony K.; Anderson, Oren P.; Strauss, Steven H.

doi:10.1021/ic00286a010

Cited by 44 publications

(24 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The same conclusion can be drawn by evaluating the AB 4 X spin system in the 19 F NMR spectrum . Especially the differnce between δ FA and δ FB of 18.2 ppm is comparable to those of [(PS)H](OTeF 5 ) of 17.4 ppm (PS = protone sponge = 1,8‐bis(dimethylamino) naphthalene) . The methyl groups show two discrete resonances in the NMR spectra due to hindered rotation around the C–C bond between the ring and the isopropyl groups shown by 2D NMR ( 1 H, 1 H‐COSY, 1 H, 13 C‐HMQC, 1 H, 13 C‐HMBC, see Figures S1–S3, Supporting Information).…”

Section: Resultssupporting

confidence: 60%

Investigation of Organonickel‐Pentafluoroorthotellurates

Hämmerling

Mann

Steinhauer

et al. 2018

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

show abstract

Section: Resultssupporting

confidence: 60%

Investigation of Organonickel‐Pentafluoroorthotellurates

Hämmerling

Mann

Steinhauer

et al. 2018

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

show abstract

“…In contrast to the EF 6 ligands, the angles in the OEF 5 ligands are all close to ideal octahedral, as is well known for the coordinated ligand [31] (in the free anions, the O-E-F eq angles tend to be closer to 958 [35] ). A slight lengthening of EÀF distances for equatorial fluorine atoms involved in secondary coordination to mercury is again apparent (see above).…”

mentioning

confidence: 66%

Can Weakly Coordinating Anions Stabilize Mercury in Its Oxidation State +IV?

Riedel

Straka

Kaupp

2005

Chemistry A European J

View full text Add to dashboard Cite

While the thermochemical stability of gas-phase HgF4 against F2 elimination was predicted by accurate quantum chemical calculations more than a decade ago, experimental verification of "truly transition-metal" mercury(IV) chemistry is still lacking. This work uses detailed density functional calculations to explore alternative species that might provide access to condensed-phase Hg(IV) chemistry. The structures and thermochemical stabilities of complexes Hg(IV)X4 and Hg(IV)F2X2 (X- = AlF4-, Al2F7-, AsF6-, SbF6-, As2F11-, Sb2F11-, OSeF5-, OTeF5-) have been assessed and are compared with each other, with smaller gas-phase HgX4 complexes, and with known related noble gas compounds. Most species eliminate F2 exothermically, with energies ranging from only about -60 kJ mol(-1) to appreciable -180 kJ mol(-1). The lower stability of these species compared to gas-phase HgF4 is due to relatively high coordination numbers of six in the resulting Hg(II) complexes that stabilize the elimination products. Complexes with AsF6 ligands appear more promising than their SbF6 analogues, due to differential aggregation effects in the Hg(II) and Hg(IV) states. HgF2X2 complexes with X- = OSeF5- or OTeF5- exhibit endothermic fluorine elimination and relatively weak interactions in the Hg(II) products. However, elimination of the peroxidic (OEF5)2 coupling products of these ligands provides an alternative exothermic elimination pathway with energies between -120 and -130 kJ mol(-1). While all of the complexes investigated here thus have one exothermic decomposition channel, there is indirect evidence that the reactions should exhibit nonnegligible activation barriers. A number of possible synthetic pathways towards the most interesting condensed-phase Hg(IV) target complexes are proposed.

show abstract

“…Structural studies at low temperature on this protonated proton sponge, performed for various salts (Kanters, Schouten, Duisenberg et al, 1991;Kanters, Schouten, Kroon & Grech, 1991;Kanters, Horst et al, 1992;Mallinson et al, 1997;Miller et al, 1988) (Kanters, Schouten et al, 1992) fairly short N--H distances of 0.94 (6) and 0.97 (6)A for two independent DMANH ÷ ions are found. A neutron study at 100 K gives an N--H distance of 1.106 (5)~, (Wozniak et al, 1996).…”

Section: Commentmentioning

confidence: 93%