Hilke Wolf

A Stable Singlet Biradicaloid Siladicarbene: (L:)2Si

Silicon, the congener of carbon, frequently shows different chemistry than that of its sister element. It has been realized that silicon prefers a positive charge if bonded to a more electronegative atom. Compounds with silicon in lower oxidation states are very important, since they can activate small organic molecules which cannot be activated by transition metals. In 2008 Robinson et al. reported on the adduct of two N-heterocyclic carbene (NHC) molecules with disilicon A (Scheme 1). This unusual compound was prepared

Stabilization of low valent silicon fluorides in the coordination sphere of transition metals.

Silicon(II) fluoride is unstable; therefore, isolation of the stable species is highly challenging and was not successful during the last 45 years. SiF(2) is generally generated in the gas phase at very high temperatures (~1100-1200 °C) and low pressures and readily disproportionates or polymerizes. We accomplished the syntheses of stable silicon(II) fluoride species by coordination of silicon(II) to transition metal carbonyls. Silicon(II) fluoride compounds L(F)Si·M(CO)(5) {M = Cr (4), Mo (5), W(6)} (L = PhC(NtBu)(2)) were prepared by metathesis reaction from the corresponding chloride with Me(3)SnF. However, the chloride derivatives L(Cl)Si·M(CO)(5) {M = Cr (1), Mo (2), W(3)} (L = PhC(NtBu)(2)) were prepared by the treatment of transition metal carbonyls with L(Cl)Si. Direct fluorination of L(Cl)Si with Me(3)SnF resulted in oxidative addition products. Compounds 4-6 are stable at ambient temperature under an inert atmosphere of nitrogen. Compounds 4-6 were characterized by NMR spectroscopy, EI-MS spectrometry, and elemental analysis. The molecular structures of 4 and 6 were unambiguously established by single-crystal X-ray diffraction. Compounds 4 and 6 are the first structurally characterized fluorides, after the discovery of SiF(2) about four and a half decades ago.

Easy Access to Silicon(0) and Silicon(II) Compounds

Two different synthetic methodologies of silicon dihalide bridged biradicals of the general formula (L(n)•)2SiX2 (n = 1, 2) have been developed. First, the metathesis reaction between NHC:SiX2 and L(n): (L(n): = cyclic akyl(amino) carbene in a 1:3 molar ratio leads to the products 2 (n = 1, X = Cl), 4 (n = 2, X = Cl), 6 (n = 1, X = Br), and 7 (n = 2, X = Br). These reactions also produce coupled NHCs (3, 5) under C-C bond formation. The formation of the coupled NHCs (L(m) = cyclic alkyl(amino) carbene substituted N-heterocyclic carbene; m = 3, n = 1 (3) and m = 4, n =2 (5)) is faster during the metathesis reaction between NHC:SiBr2 and L(n): when compared with that of NHC:SiCl2. Second, the reaction of L(1):SiCl4 (8) (L(1): =:C(CH2)(CMe2)2N-2,6-iPr2C6H3) with a non-nucleophilic base LiN(iPr)2 in a 1:1 molar ratio shows an unprecedented methodology for the synthesis of the biradical (L(1)•)2SiCl2 (2). The blue blocks of silicon dichloride bridged biradicals (2, 4) are stable for more than six months under an inert atmosphere and in air for one week. Compounds 2 and 4 melt in the temperature range of 185 to 195 °C. The dibromide (6, 7) analogue is more prone to decomposition in the solution but comparatively more stable in the solid state than in the solution. Decomposition of the products has been observed in the UV-vis spectra. Moreover, compounds 2 and 4 were further converted to stable singlet biradicaloid dicarbene-coordinated (L(n):)2Si(0) (n = 1 (9), 2 (10)) under KC8 reduction. Compounds 2 and 4 were also reduced to dehalogenated products 9 and 10, respectively when treated with RLi (R = Ph, Me, tBu). Cyclic voltametry measurements show that 10 can irreversibly undergo both one electron oxidation and reduction.

Influence of Donor-Acceptor Distance Variation on Photoinduced Electron and Proton Transfer in Rhenium(I)-Phenol Dyads

A homologous series of four molecules in which a phenol unit is linked covalently to a rhenium(I) tricarbonyl diimine photooxidant via a variable number of p-xylene spacers (n = 0-3) was synthesized and investigated. The species with a single p-xylene spacer was structurally characterized to get some benchmark distances. Photoexcitation of the metal complex in the shortest dyad (n = 0) triggers release of the phenolic proton to the acetonitrile/water solvent mixture; a H/D kinetic isotope effect (KIE) of 2.0 ± 0.4 is associated with this process. Thus, the shortest dyad basically acts like a photoacid. The next two longer dyads (n = 1, 2) exhibit intramolecular photoinduced phenol-to-rhenium electron transfer in the rate-determining excited-state deactivation step, and there is no significant KIE in this case. For the dyad with n = 1, transient absorption spectroscopy provided evidence for release of the phenolic proton to the solvent upon oxidation of the phenol by intramolecular photoinduced electron transfer. Subsequent thermal charge recombination is associated with a H/D KIE of 3.6 ± 0.4 and therefore is likely to involve proton motion in the rate-determining reaction step. Thus, some of the longer dyads (n = 1, 2) exhibit photoinduced proton-coupled electron transfer (PCET), albeit in a stepwise (electron transfer followed by proton transfer) rather than concerted manner. Our study demonstrates that electronically strongly coupled donor-acceptor systems may exhibit significantly different photoinduced PCET chemistry than electronically weakly coupled donor-bridge-acceptor molecules.

Phase Transition of [2,2]‐Paracyclophane – An End to an Apparently Endless Story

In this contribution, the solid-state low-temperature phase structure of [2,2]-paracyclophane is unambiguously characterised by single-crystal X-ray analysis. Additionally, a heat capacity measurement was undertaken, which proves the existence of a λ-type phase transition at 45 K, a transition that is connected with the formation of a secondary Cp/T feature at 60 K. The low-temperature phase (<45 K) crystallises in the lower symmetry space group P4n2, whereas the high-temperature phase (>60 K) crystallises in space group P4(2)/mnm. This proves what has been postulated both by experimental and theoretical chemists but has repeatedly been dismissed as speculation many times.

Charge density investigations on [2,2]-paracyclophane – in data we trust.

Four datasets on [2,2]-paracyclophane were collected in-house and at the Advanced Photon Source at two different temperatures for charge density investigation. Global data quality indicators such as high resolution, high I/σ(I) values, low merging R values and high multiplicity were matched for all four datasets. The structural parameters did not show significant differences, but the synchrotron data depicted deficiencies in the topological analysis. In retrospect these deficiencies could be assigned to the low quality of the innermost data, which could have been identified by e.g. merging R values for only these reflections. In the multipole refinement these deficiencies could be monitored using DRK-plot and residual density analysis. In this particular example the differences in the topological parameters were relatively small but significant.

Direct Spectroscopic Evidence of the Mechanism behind the Phase Transition of [2,2]‐Paracyclophane

[2,2]-Paracyclophane undergoes phase transitions at 45 and 60 K. Based on simultaneous Raman spectroscopy and inelastic neutron scattering experiments (12-70 K), it was shown that a twisting motion of the ethylene bridge perpendicular to the plane of the aromatic rings drives the phase transition. The low-temperature (<45 K) and high-temperature (>60 K) conformers only differ by this twisting motion, which freezes out below 45 K and is thermally averaged above 60 K. Between 45 and 60 K, the system gains energy until the phase transition is complete.