Lewis acid-base adducts of zwitterionic alkali metal methanides and silanides with BH3

The synthesis, structures and spectroscopic properties of M(MeOCH₂CH₂OMe₂Si)₃CBH₃ (M-1-BH₃) and M(MeOCH₂CH₂OMe₂Si)₃SiBH₃ (M-2-BH₃) (M?=?Li, Na, K) derived from reactions of BH₃ with the alkali metal zwitterions [M(MeOCH₂CH₂OMe₂Si)₃C] (M-1) and [M(MeOCH₂CH₂OMe₂Si)₃Si] (M-2) (M?=?Li, Na, K), resp., are reported. X-ray analysis and DFT calculations reveal discrete zwitterionic structures with the octahedral alkali metal cations rigidly locked and charge separated from the BH₃ units via pendant donors groups. Solution experiments with the hydride acceptors B(C₆F₅)₃ and [Ph₃C]₂[B₁₂C₁₂] indicate that Na-1-BH₃ can donate hydrides to form cations of formula [Na(MeOCH₂CH₂OMe₂Si)₃CBH₂]⁺.     

Nuclear inelastic scattering spectroscopy of iron-sulfur cubane compounds

The potential of NIS spectroscopy to study the iron-sulfur clusters in metalloproteins is illustrated using model compounds. The origin of the intense low energy transfer bands is discussed.     

The hyperfine coupling tensors of muonated radicals in single‐crystal benzophenone

The hyperfine coupling tensors of muonated radicals in a large single crystal of benzophenone have been determined by measuring the hyperfine couplings of the radicals as the crystal was rotated about three orthogonal axes. Signals from four radicals were observed, corresponding to the four molecules per unit cell in the crystal. Due to an ambiguity in the data we are unable to discriminate between two similar hyperfine coupling tensors. Both lead to an isotropic hyperfine coupling of \sim32 MHz, contrasting with the solution value of 42 MHz obtained earlier in diethyl ether. The anisotropic components of the tensor are relatively large, at approximately -15 MHz, -6 MHz and 21 MHz, respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

Molecular dynamics of organometallic compounds using μSR

The potential of μSR in the investigation of molecular dynamics of organometallic compounds is illustrated with applications to the classic metallocene compound, ferrocene. Muonium addition gives two radicals in this case with the slowly relaxing radical showing a repolarisation curve corresponding to a hyperfine field of ca. 200 G suggesting addition to the cyclopentadienyl ring. The temperature dependence of the relaxation of this radical gives an activation energy of ca. 5.4 kJ/mol, in good agreement with QENS and NMR estimates for cyclopentadienyl, ring rotation in this compound.     

Electronic interaction in an outer-sphere mixed-valence double salt: a polarized neutron diffraction study of K(3)(MnO(4))(2)

The mixed-valence double salt K(3)(MnO(4))(2) crystallizes in space group P2(1)/m with Z = 2. The manganese centers Mn1 and Mn2 constitute discrete "permanganate", [Mn(VII)O(4)](-), and "manganate", [Mn(VI)O(4)](2-), ions, respectively. There is a spin-ordering transition to an antiferromagnetic state at ca. T = 5 K. The spin-density distribution in the paramagnetic phase at T = 10 K has been determined by polarized neutron diffraction, confirming that unpaired spin is largely confined to the nominal manganate ion Mn2. Through use of both Fourier refinement and maximum entropy methods, the spin on Mn1 is estimated as 1.75 +/- 1% of one unpaired electron with an upper limit of 2.5%.     

Analysis of the Symmetry of Crystal Packing Forces by Methyl Proton Tunneling: A Strategy for the Unambiguous Assignment of the Magnetic Jahn – Teller Effect in Molecules

Intrinsic and extrinsic forces behind the distortion in metal atom clusters can be readily distinguished provided that the clusters are embedded in a suitable ligand environment and that the tunneling of the protons in the peripheral ligands is then analyzed by inelastic neutron scattering. For the [Cr₃O(OOCCH₃)₆(H₂O)₃]Cl⋅6 H₂O model system studied, the tunneling process is very sensitive to the local environment. Thus a tool is available to allow a better assessment of the cause of structural distortions.     

Muon spin rotation (μSR) in a metal-cluster carbonyl compound

μSR spectra from a metal carbonyl compound are reproted for the first time. The metal cluster compound Cs₂[Os₁₀C(CO)₂₄] shows a temperature dependent signal for implanted muons with the onset of motional narrowing at ca. 200 K. Also observed is a probable change in the width within the temperature range 40–140 K. A tentative assignment is provided for the muon sites.