In this paper we discuss the structural chemistry of (PPh(4))(2)M(WS(4))(2) (M = Co, Ni, Zn) materials. For M = Ni we and others have been unable to grow single crystals and we report the structure determination from powder diffraction. The material is triclinic (P1, a = 9.3730(2), b = 12.4951(3), c = 12.5189(3) A, alpha = 65.814(1), beta = 83.751(1), gamma = 69.571(1) degrees at T = 293 K). It...

An !-word p over a nite alphabet is called disjunctive if every nite word over occurs as a subword in p. A real number is called disjunctive to base a if it has a disjunctive a-adic expansion. For every pair of integers a; b 2 such that there exist numbers disjunctive to base a but not to base b we explicitly construct very simple examples of such numbers. General versions of the following resu...

The transition metal catalyzed ethylene polymerization in aqueous emulsion has been increasingly successful in the last couple of years. Water however adversely affects the polymerization process by (a) competing with ethylene for the binding site at the metal and (b) hydrolyzing the growing chain. Neutral salicylaldiminato and cationic diimine complexes of Ni and Pd with different substituent ...

Modification of the metal's electronic environment by ligand association and dissociation in metalloenzymes is considered cardinal to their catalytic activity. We have recently presented a novel system that utilizes the bacteriochlorophyll (BChl) macrocycle as a ligand and reporter. This system allows for charge mobilization in the equatorial plane and experimental estimate of changes in the el...

The optical properties of the dmit ion (dmits4,5-dimercapto-1,3-dithiol-2-thiolate) have been characterized under a range of conditions. The oxidatively sensitive anion is highly solvatochromic: lmaxs504 (H2O), 514 (MeOH), 568 (MeCN), and 632 nm (DMF). With a shift in absorption maximum of 4000 cm (DMF versus H2O), dmit 2y is possibly the most solvatochromic species known. The dianion is monopr...

Intermolecular arene C-H activation mediated by a divalent nickel species under extremely mild conditions is described. The reactions of either Ni(COD)2 with H[N(o-C6H4PR2)2] (H[R-PNP]; R = iPr, Cy) in benzene at room temperature or [R-PNP]NiCl with LiBHEt3 in THF at -35 degrees C produced the corresponding [R-PNP]NiH in high yield. Addition of 1 equiv of B(C6F5)3 to a benzene solution of [R-PN...

We introduce a generalized bootstrap technique for estimators obtained by solving estimating equations. Some special cases of this generalized bootstrap are the classical bootstrap of Efron, the deleted jackknife and variations of the Bayesian bootstrap. The use of the proposed technique is discussed in some examples. Distributional consistency of the method is established and an asymptotic rep...

Let A,B be nonempty subsets of a an abelian group G. Let Ni(A,B) denote the set of elements of G having i distinct decompositions as a product of an element of A and an element of B. We prove that ∑ 1≤i≤t |Ni(A,B)| ≥ t(|A|+ |B| − t− α+ 1 + w) − w, where α is the largest size of a coset contained in AB and w = min(α − 1, 1), with a strict inequality if α ≥ 3 and t ≥ 2, or if α ≥ 2 and t = 2. Thi...

By reaction of K2[S2C N S 02C6H 5] • 2 H 20 and K2[S2C N S O ,Q H 4Cl] ■ 2 H .O , respectively, with N i(CH,COO)2 • 4 H 20 the complex anions [Ni(S2C = N -S Ö 2C hH 5)2]2 ' and [Ni(S2C = N S 0 2C hH4C l) 2]2~ are formed and have been isolated in form of their (PPh4) salts. (PPh4)2[Ni(S2C =N —S 0 2—Ph)2] crystallizes monoclinicly. space group P2,/ö with a = 19.081(4), b = 9.106(1), c = 17.630(4)...

We report the first anion photoelectron spectroscopic study of nickel monoxide ~NiO!, nickel dioxide ~ONiO!, and nickel-O2 complex, Ni~O2!. The adiabatic electron affinity ~EA! of NiO is measured to be 1.46 ~2! eV. Five low-lying electronic excited states (A P , a D , B F , b S, c P) are observed for NiO at 0.43 ~4!, 0.94 ~4!, 1.24 ~3!, 1.80 ~10!, and 2.38 ~10! eV above the ground state, respec...