A stable discrete nickel borohydride complex (Tp*NiBH(4) or Tp*NiBD(4)) was prepared using the nitrogen-donor ligand hydrotris(3,5-dimethylpyrazolyl)borate (Tp*-). This complex represents one of the best characterized nickel(II) borohydrides to date. Tp*NiBH(4) and Tp*NiBD(4) are stable toward air, boiling water, and high temperatures (mp > 230 degrees C dec). X-ray crystallographic measurements for Tp*NiBH(4) showed a six-coordinate geometry for the complex, with the nickel(II) center facially coordinated by three bridging hydrogen atoms from borohydride and a tridentate Tp(-) ligand. For Tp*NiBH(4), the empirical formula is C(15)H(26)B(2)N(6)Ni, a = 13.469(9) A, b = 7.740(1) A, c = 18.851(2) A, beta = 107.605(9) degrees, the space group is monoclinic P2(1)/c, and Z = 4. Infrared measurements confirmed the presence of bridging hydrogen atoms; both nu(B[bond]H)(terminal) and nu(B[bond]H)(bridging) are assignable and shifted relative to nu(B-D) of Tp*NiBD(4) by amounts in agreement with theory. Despite their hydrolytic stability, Tp*NiBH(4) and Tp*NiBD(4) readily reduce halocarbon substrates, leading to the complete series of Tp*NiX complexes (X = Cl, Br, I). These reactions showed a pronounced hydrogen/deuterium rate dependence (k(H)/k(D) approximately 3) and sharp isosbestic points in progressive electronic spectra. Nickel K-edge X-ray absorption spectroscopy (XAS) measurements of a hydride-rich nickel center were obtained for Tp*NiBH(4), Tp*NiBD(4), and Tp*NiCl. X-ray absorption near-edge spectroscopy results confirmed the similar six-coordinate geometries for Tp*NiBH(4) and Tp*NiBD(4). These contrasted with XAS results for the crystallographically characterized pseudotetrahedral Tp*NiCl complex. The stability of Tp*Ni-coordinated borohydride is significant given this ion's accelerated decomposition and hydrolysis in the presence of transition metals and simple metal salts.

Monomeric five-coordinate nickel−cysteine complexes were prepared using anionic tris(3,5-disubstituted pyrazolyl)borates (Tp* - and TpPhMe-) and l-cysteine (ethyl ester and amino acid forms). Tp*NiCysEt crystallizes with a single methanol of solvation in the monoclinic space group P21:  a = 7.8145(18), b = 24.201(6), c = 7.9925(14) Å; β = 117.991(16)°. [Tp*NiCys-][K+] and TpPhMeNiCysEt show magnetic and electronic characteristics similar to Tp*NiCysEt, so that the trigonal bipyramidal coordination geometry confirmed for Tp*NiCysEt in the solid state likely applies to all three. All three complexes have high spin magnetic ground states at room temperature (μeff = 2.9−3.2 μB, S =1). Their electronic spectra are dominated by sulfur to nickel charge-transfer bands (388−430 nm in chloroform) with energies that correlate to respective thiolate basicities and TpX- donor strengths. The Tp* derivatives undergo a rapid reaction with molecular oxygen. Stoichiometric, infrared, and electronic spectroscopy measurements are consistent with formation of a sulfinate as a result of reaction with dioxygen. Kinetics measurements for the reaction of Tp*NiCysEt and O2 fit the following composite rate law:  rate = k 1[Tp*NiCysEt] + k 2[O2][Tp*NiCysEt] with k 1 = 0.013(1) min-1 and k 2 = 4.8(1) M-1·min-1 at 22 °C. Increased nucleophilicity of the nickel−sulfur center enhanced by electron donation from Tp*- (vs TpPhMe-) and encouraged by a trigonal bipyramidal geometry (vs square planar Ni(CysEt)2) is hypothesized as the reason for the susceptibility of Tp*NiCys complexes to oxygen.

A novel non-invasive technique for monitoring fluid content in the human bladder is described. Specifically, a precommercial electric impedance tomograph (EIT) was applied to measure and visualize impedance changes in the lower torso due to changes in bladder volume. Preliminary measurements were conducted during routine urodynamic tests of nine male paraplegic patients, in whom a contrast agent was slowly infused into the bladder for diagnostic purposes. In some patients, a good correlation between bladder volume and EIT measurements was found, whereas in others the correlation was still good but inverted, presumably due to a poor electrode positioning. These preliminary results indicate that a sufficiently accurate finite element modeling of the impedance distribution in the abdomen, and proper electrode positioning aids, are important prerequisites to enable this technology to be used for routine measurement of bladder volume.

Patients with chronic heart failure (CHF) often suffer from the formation of edema within their body. To monitor the appearance of such edema in lung and limbs as early as possible would improve the medical treatment fundamentally. Bioimpedance-Spectroscopy is a non-invasive, easyto-implement measurement method that allows determining the water content of a patient. However, stable long term measurements are difficult to perform and so the optimal measurement conditions have to be defined precisely. In the past, a lot of work was focused on the development of the optimal measurement setup that allows stable and reproducible longterm monitoring of edema. Based on these investigations, a measurement protocol was developed and within this study, case reports shall be presented in which five patients suffering from acutely decompensated CHF were monitored during their complete medical treatment in the clinic. Every day, the whole body-and thoracic impedance were measured to monitor the progress of edema in the limbs and lung, respectively.