Organonickel(II) Complexes with Anionic N-Donor Ligands. Hydration of coordinated nitriles at a nickel(II) site

The hydroxo complex (Bu₄N)₂[Ni₂(C₆F₅)₄(μ-OH)₂]reacts with 2,3,4,5,6-pentafluoro benzenamine (C₆F₅-NH₂), 1,3-diaryltriaz-1-enes (ArNH? N=N? Ar, Ar = Ph, 4-MeC₆H₄, 4-MeOC₆H₄), 7-aza-1H-indole (= 1H-pyrrolo[2.3-b]pyridine; Hazind), N-phenylpyridin-2-amine(pyNHPh), and N-phenylpyridine-2-carboxamide (py-CONHPh) at room temperature in acetone to give the binuclear complexes (Bu₄N)₂[Ni₂(C₆F₅)₄(μ-C₆F₅NH)₂] ( 1 ) and (Bu₄N)₂[{Ni(C₆F₅)₂} 2(μ-OH)(μ-azind)] ( 2 ) and the mononuclear complexes Bu₄N[Ni(C₆F₅)2(ArN₃Ar)] ( 3 – 5 ), Bu₄N[Ni(C₆F₅)₂(pyNPh)] ( 6 ), and Bu₄N[Ni(C₆F₅)₂(pyCONPh)] ( 7 ). The hydroxo.complex (Bu₄N)₂[{Ni(C₆F₅)2-(μ-OH)}₂] promotes the nucleophilic addition of water to pyridine-2-carbonitrile, 2-aminoacetonitrile, and 2-(dimethylamino)acetonitrile, and complexes 8 – 10 containing pyridine-2-carboxamidato, 2-aminoacetamidato and 2-(dimethylamino)acetamidato ligands are formed. Analytical (C, H, N) and spectroscopic (IR, ¹H and ¹⁹F-NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of (Bu₄N)₂[{Ni(C₆F₅)₂}₂(μ-OH)(μ-azind)] ( 2 ) established the binuclear nature of the anion; the two Ni-atoms are bridged by an OH group and a 7-aza-7H-indol-7-yl group, but the central Ni? O? Ni? N? C? N ring is not planar, the dihedral angle between the Ni? O? Ni and Ni? N? C? N? Ni planes being 84.4°.     

Graphs whose every transitive orientation contains almost every relation

Given a graphG onn vertices and a total ordering ≺ ofV(G), the transitive orientation ofG associated with ≺, denotedP(G; ≺), is the partial order onV(G) defined by settingx<y inP(G; ≺) if there is a pathx=x ₁ x ₂…x _r=y inG such thatx ₁ ≺x _j for 1≦i<j≦r. We investigate graphsG such that every transitive orientation ofG contains ₂ ⁿ −o(n ²) relations. We prove that almost everyG _n,p satisfies this requirement if , but almost noG _n,p satisfies the condition if (pn log log logn)/(logn log logn) is bounded. We also show that every graphG withn vertices and at mostcn logn edges has some transitive orientation with fewer than ₂ ⁿ −δ(c)n ² relations. Partially supported by MCS Grant 8104854.     

The spectrum of a quasiperiodic Schrödinger operator

The spectrum (H) of the tight binding Fibonacci Hamiltonian (H _mn= _m,n+1+ _m+1,n + _m,n v(n),v(n)= ((n–1)), 1/ is the golden number) is shown to coincide with the dynamical spectrum, the set on which an infinite subsequence of traces of transfer matrices is bounded. The point spectrum is absent for any , and (H) is a Cantor set for 4. Combining this with Casdagli's earlier result, one finds that the spectrum is singular continuous for 16.On leave from the Central Research Institute for Physics, Budapest, Hungary     

Elementary operators with H∞-symbols

Let T be a c.n.u. contraction on a Hilbert spaceH and let u-(u₁,...,u_n) be an n-tuple of H(T). We calculate various joint spectra of u(T) and apply the results to study the spectral and index theories of elementary operators associated with n-tuples of the above type.Both authors have been partially supported by NSF grants.     

Estimation of density functions by order statistics

The properties of the empirical density function,f _n(x) = k/n( _j ⁺ – _j-1 ⁺ ) if _j-1 ⁺ < x ⁺ where _j-1 ⁺ and _j ⁺ are sample elements and there are exactlyk – 1 sample elements between them, are studied in that practical point of view how to choose a suitablek for a good estimation. A bound is given for the expected value of the absolute value of difference between the empirical and theoretical density functions.     

Problems and results on additive properties of general sequences,V

A very special case of one of the theorems of the authors states as follows: Let 1a ₁a ₂... be an infinite sequence of integers for which all the sumsa _i +a _j , 1ij, are distinct. Then there are infinitely many integersk for which 2k can be represented in the forma _i +a _j but 2k+1 cannot be represented in this form. Several unsolved problems are stated.Dedicated to our friend Professor E. Hlawka on the occasion of his seventieth birthday     

Single-step preparation and catalytic activity of mesoporous MCM-41 and SBA-15 silicas functionalized with perfluoroalkylsulfonic acid groups analogous to Nafion

Preparation of hybrid organic-inorganic MCM-41 and SBA-15 silicas functionalized with perfluoroalkylsulfonic acid groups has been achieved in a single step by reacting the mesoporous silicas with 1,2,2-trifluoro-2-hydroxy-1-trifluoromethylethane sulfonic acid beta-sultone; the catalysts showed higher activity than commercial Nafion-silica composite for the esterification of long chain fatty acids with ethanol.     

Change of geometry of polyacetylene upon charge transfer

Crystal orbital calculations on cis- and trans-polyacethylene chains indicate two kinds of geometry changes on charge transfer. (1) increase (decrease) of the CC bond lenght and CCC bond angles in the trans conformer taking up (losing) electrons, and $\text{(u)}\text{?}$ a tendency towards bond-length equalization on electron uptake and loss for both conformers.