Chemistry of Diruthenium and Dirhodium Analogues of Pentaborane(9): Synthesis and Characterization of Metal N,S‐Heterocyclic Carbene and B‐Agostic Complexes

Building upon our earlier results on the synthesis of electron‐precise transition‐metal–boron complexes, we continue to investigate the reactivity of pentaborane(9) and tetraborane(10) analogues of ruthenium and rhodium towards thiazolyl and oxazolyl ligands. Thus, mild thermolysis of nido‐[(Cp*RuH)₂B₃H₇] ( 1 ) with 2‐mercaptobenzothiazole (2‐mbtz) and 2‐mercaptobenzoxazole (2‐mboz) led to the isolation of Cp*‐based (Cp*=η⁵‐C₅Me₅) borate complexes 5 a , b [Cp*RuBH₃L] ( 5 a : L=C₇H₄NS₂; 5 b : L=C₇H₄NOS)) and agostic complexes 7 a , b [Cp*RuBH₂(L)₂], ( 7 a : L=C₇H₄NS₂; 7 b : L=C₇H₄NOS). In a similar fashion, a rhodium analogue of pentaborane(9), nido‐[(Cp*Rh)₂B₃H₇] ( 2 ) yielded rhodaboratrane [Cp*RhBH(L)₂], 10 (L=C₇H₄NS₂). Interestingly, when the reaction was performed with an excess of 2‐mbtz, it led to the formation of the first structurally characterized N,S‐heterocyclic rhodium‐carbene complex [(Cp*Rh)(L₂)(1‐benzothiazol‐2‐ylidene)] ( 11 ) (L=C₇H₄NS₂). Furthermore, to evaluate the scope of this new route, we extended this chemistry towards the diruthenium analogue of tetraborane(10), arachno‐[(Cp*RuCO)₂B₂H₆] ( 3 ), in which the metal center possesses different ancillary ligands.     

Hypergroups and polygroups in diffeology

Abstract

We introduce diffeological algebraic hyperstructures such as diffeological hypergroups and diffeological polygroups, which are generalizations of diffeological groups. After providing some examples of these notions, we investigate the relationships between diffeological hypergroups and diffeological groups. It is proved that there is an equivalence of categories between subductions over diffeological groups and diffeological complete hypergroups. We finally show how every diffeological polygroup is a subpolygroup of a diffeological poly-monoid of hyper-diffeomorphisms.

Communicated by J. L. Gomez Pardo     

Supersymmetry and the ladder operator technique in quantum mechanics: The radial Schrödinger equation

Using the ladder operator technique, a construction of the supersymmetric Hamiltonian is proposed. We show that the accidental degeneracies associated with the Coulomb and isotropic oscillator problems may be attributed to the existence of a supersymmetry of the Hamiltonians.     

Crystal structure of form 1, magnetic properties and polymorphism of bis (NN-di-(n-propyl)dithiocarbamato iron (III) iodide

The crystal structure of bis (NN-di(n-propyl)dithiocarbamato iron(III) iodide, Fe^III(S₂CN₆H₁₄)₂I, has been determined by the heavy-atom method and refined toR=0.055 for 3487 reflections withI(hkl)>3I(hkl). The crystals are triclinic,C¯1,Z=8,a=27.644(6),b=19.186(4),c=8.694(2) Å,=87.79(1),=88.72(1), =101.87(2)°. The I-Fe bond lengths are different in the two moleculesA andB in the asymmetric unit, having values of 2.642 Å (2.655) and 2.612 Å (2.634) respectively (libration-corrected values given in parentheses). The measured effective magnetic moment _eff3.89 BM, independent of temperature (93-353K), suggests a spinS of 3/2 with three unpaired electrons for Fe^III.     

Ion Association and Solvation Behavior of Some 1-1 Electrolytes in 2-Ethoxyethanol Probed by a Conductometric Study

Precise measurements of the electrical conductances of solutions of potassium thiocyanate (KCNS), ammonium thiocyanate (NH₄CNS), sodium nitrate (NaNO₃) and ammonium nitrate (NH₄NO₃) in 2-ethoxyethanol (EE) at temperatures 35, 40, 45 and 50,^∘C are reported. The conductance data have been analyzed by the 1978 Fuoss conductance equation. A thermodynamic analysis of the ionic association processes has also been made and the Coulombic forces are found to play a major role in the association processes. The ionic contributions to the limiting equivalent conductances have been determined using the reference electrolyte method. Strong association was found for all these electrolytes in this solvent medium. The cations are found to be substantially solvated in 2-ethoxyethanol, whereas the anions appear to have only weak interaction with the solvent molecules.     

Neutron diffraction experiments on CsCrI3 at 300, 77, and 1.2°K: H. W. Zandbergen and D. J. W. Ijdo. Gorlaeus Laboratories,University of Leiden,P.O. Box 9502, 2300 RA Leiden,The Netherlands

The orthorhombic α-PbO₂ phase of FeNbO₄ was prepared and its photoelectronic properties measured: Sintered disks were shown to be n type and gave a resistivity of 40 Ω-cm. Measurements of the photoresponse gave a flat-band potential between 0.1 and 0.4 V vs SCE at a pH of 8.5 and an optical band gap of 2.08(2) eV. Several higher-energy band gaps at 2.68(2), 2.94(2), 3.24(2), and 4.38(2) eV were also determined. There appears to be an enhancement of the quantum efficiency due to the presence of [FeO₆] active centers while retaining the fundamental characteristics of the [NbO₆] octahedra.     

Mixed-ligand complexes of osmium(III)/(IV) 8-quinolinolates: synthesis,characterization and redox behaviour

Summary A group of mixed-tris chelates of osmium(III) and osmium(IV) of type [OsAQ₂]^{0/1 +} [HA = glycine (glyH), picolinic acid (PicH) and quinaldic acid (qndH); HQ = 8-quinolinol] were prepared and characterized by physicochemical, magnetic and spectroscopic methods. The complexes exhibit several spin-allowed and spin-forbidden absorption bands and shoulders in the 200–700 nm region. The new chelates are electroactive and display nearly reversible Os^IV-Os^III and Os^III-Os^II couples in the ca. –1.1 to +0.3 V range versus s.c.e. The stability of metal oxidation states is discussed in terms of the electrochemical results.     

An all-optical integrated system for implementing arithmetic operation in 2’s complement method with the active participation of non-linear material based switches

Optics is regarded undoubtedly a potential and successful candidate in information and data processing because of its inherent parallelism. In last few decades several all-optical data processors, algebraic processors, arithmetic processors are proposed. Here in this communication the authors propose a completely new scheme for implementing binary data arithmetic in 2’s Complement method which is the most advantageous among all other established subtraction methods. To implement it we use non-linear material massively.