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Konrad Seppelt

Publications and source records attributed to Konrad Seppelt.

8 recordsLinked to original sources
PubMed2004

First detection of a selenenyl fluoride ArSe-F by NMR spectroscopy: the nature of Ar2Se2/XeF2 and ArSe-SiMe3/XeF2 reagents.

Arylselenenyl fluorides ArSeF are obtained from diselenides Ar2Se2 or arylselenotrimethylsilanes ArSe-SiMe3, and XeF2. They are detected by low-temperature 19F and 77Se NMR spectroscopy. Substitution in the ortho position of the aromatic ring to provide electronic or steric protection is a requirement for their formation. ArSe--F compounds decompose according to 3 ArSe-F-->[ArSe-SeF2Ar]+ArSe-F-->ArSeF3+Ar2Se2. Reaction energies for this disproportionation as well as that of the sulfur and tellurium homologues have been calculated with MP2, CCSD(T,) and B3 LYP methods. They were found to be increasingly exothermic in the sequence S<Se<Te. For selected Se-C and Se-F compounds the 77Se and 19F chemical shifts have been calculated by GIAO-MP2 and GIAO-B3 LYP methods and are in good agreement with experimental values.

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PubMed2004

MoF6 and WF6: nonrigid molecules?

Calculations reveal that the octahedral-trigonal prismatic-octahedral rearrangement has particularly low-energy barriers for MoF6, WF6, and (hypothetical) CrF6. Experimental evidence is obtained from the dynamic 19F NMR spectra of the derivatives CF3-CH2-O-MoF5, CF3-CH2-O-WF5, C6F5-O-MoF5, C6F5-O-WF5, and (CF3)3C-O-WF5. The ground-state structure of all these compounds is octahedral; at elevated temperatures the nonequivalent metal-bound fluorine atoms undergo an intramolecular exchange. The exchange mechanism could be a 3+3 or a 2+4 twist; calculations favor the 3+3 twist.

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PubMed2003

Fluorination of [Os3(CO)12] and [Ir4(CO)12].

Fluorination of [Os(3)CO(12)] in HF/SbF(5) affords [Os(CO)(4)(FSbF(5))(2)]. According to its crystal structure (orthorhombic, Pna2(1), a = 1590.3(3), b = 1036.6(1), c = 878.2(2) pm, Z = 4), the two SbF(6) units occupy cis positions in the octahedral environment around the Os atom. Fluorination of [Ir(4)(CO)(12)] in HF/SbF(5) produced three different compounds: (1) [Ir(4)(CO)(8)(mu-F)(2)(Sb(2)F(11))(2)] (tetragonal, P4n2, a = 1285.2(2), c = 952.9(1) pm, Z = 2). Here, two of the six edges of the Ir(4) tetrahedron in [Ir(4)CO(12)] are replaced by bridging fluorine atoms. (2) [fac-Ir(CO)(3)(FSbF(5))(2)HF]SbF(6).HF (orthorhombic, Pnma, a = 1250.6(1), b = 1340.7(2), c = 1092.6(2) ppm, Z = 4). The Ir(4) tetrahedron in Ir(4)(CO)(12) is completely broken down, but the facial Ir(CO)(3) configuration is retained. (3) [mer-Ir(CO)(3)F(FSbF(5))(2)] (triclinic, P1, a = 834.9(1), b = 86 4.9(1), c = 1060.0(1) pm, alpha = 69.173(4) degrees, beta = 77.139(4) degrees, gamma = 88.856(4) degrees, Z = 2).

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PubMed2003

The platinum catalyst [bpyrPtCl2] in superacidic solution.

The methane oxidation catalyst [bpyrPtCl(2)] (bpyr = bis-pyrimidine) dissolves in superacidic HF/SbF(5) solution under formation of a dinuclear cation [H(2)bpyrPt(mu-Cl)(2)PtbpyrH(2)](6+). Two crystal forms are isolated, [Pt(2)Cl(2)bpyr(2)H(4)](6+)(SbF(6)(-))(4)(Sb(2)F(11)(-))(2).2HF (I) (triclinic, Ponemacr;, a = 814.8(2) pm, b = 1444.8(3) pm, c = 2300.5(5) pm, alpha = 89.627(4) degrees, beta = 84.285(4) degrees, gamma = 84.665(4) degrees, Z = 2) and [Pt(2)Cl(2)bpyrH(4)](6+)(Sb(2)F(11)(-))(6).4HF (II) (triclinic, Ponemacr;, a = 879.4(2) pm, b = 1170.4(3) pm, c = 1789.9(5) pm, alpha = 95.37(2) degrees, beta = 99.97(2) degrees, gamma = 100.41(2) degrees, Z = 1). The cation in I has an angle of 148.4(1) degrees between the two square plane platinum environments, while the cation in II is fully planar. The non-platinum-bound nitrogen atoms are all protonated in the superacidic medium.

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PubMed2003

Nonoctahedral structures.

There is always a special reason when six-coordinate molecules or complexes are nonoctahedral. The Jahn-Teller distortion is the longest known example. Also well understood now is the steric activity or nonactivity of a nonbonding electron pair, for example XeF(6). In the past few years, it became obvious that six-coordinate d(0) and d(1) complexes with sigma only ligands such as Mo(CH3)(6) are far from octahedral; rather, they are trigonal prismatic or even C(3v) distorted trigonal prismatic. This phenomenon can be explained with simple molecular orbital or valence bond models.

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