Ca7Au3 and Ca5Au4, two structures closely related to the Th7Fe3 and Pu5Rh4 types

Two new intermetallic compounds have been synthetized and structurally studied by single crystal diffractometric data: Ca₇Au₃ (oP80, space groupPbca,a = 20.742(8), b = 18.036(8), c = 6.665(2) A?,Z = 8, R = 0.051) and Ca₅Au₄ (mP18, space groupP2₁/c, a = 8.028(3), b = 8.019(6), c = 7.727(3) A?, β = 109.16(6)°,Z = 2, R = 0.104). Both atomic arrangements, which represent new structural types, are based on Au-centered Ca trigonal prisms and are geometrically related to the Th₇Fe₃ and Pu₅Rh₄ structures.     

Photophysical study on a new class of benzophenone containing photoinitiators of polymerization: Properties of poly(4-acryloxybenzophenone) and a model compound

The photophysical characteristics of poly 4(2-acryloxybenzophenone), poly-ABP, and its model compound 4(2-methylpropionyloxy)benzophenone, IBP, have been determined by steady state and pulse methods. In IBP the observed properties are mainly due to the n,π1 triplet of the benzophenonic moiety. In poly-ABP, the formation of singlet excimers competes with the intersystem crossing leading to benzophenonic triplet. The triplet lifetime in polymer is reduced, compared to the model compound. This fact is explained in terms of intramolecular hydrogen abstraction of the triplet.     

Reaction des lithiens avec les organophosphores. Reaction d'addition du t-butyllithium sur le noyau benzenique des sels de phenylphosphoniums

A new reaction of organolithium compounds with phosphonium salts is described; reaction of t-butyllithium with dibenzylaminophosphonium or tetraphenylphosphonium bromides takes place through addition of the t-butyl group on a benzene ring at the position para to the phosphorus atom, the ylid formed reacts in a characteristic Wittig reaction with p-tolylaldehyde.     

Advances in inorganic chemistry and radiochemistry,vol. 18: Edited by H.J. Emeléus and A.G. Sharpe,Academic Press,New York/San Francisco/London, 1976, vii + 414 pages, $35.50.

The catinic complex trans-[FeCl(CCHPh)(depe)₂]⁺ (depe = bis(diethylphosphino)ethane has been prepared by interaction of trans-[FeCl₂(depe)₂] with penylacetylene in methanol solution in the presence of NaX (X = BPh₄ or PF₆.     

Reaktionen an komplexgebundenen liganden: XXIX. Ein einfacher weg zu azomethin-komplexen: Kondensation von chrom—, molybdän—, wolfram—, mangan— und eisen—ammoniak-komplexen und ketonen zu ketimin-komplexen

Treatment of transition-metal—ammonia complexes with ketones yields complexes with RR′CNH ligands. Of particular interest is the stabilization of dialkylketimines such as e.g. (CH₃)₂CNH and C₆H₁₀NH in [M(CO)₅{NHC(CH₃)₂}] or [M(CO)₅ {NHC₆H₁₀}] (M = Cr, Mo, W). The principle of synthesis may be applied to a wide range of different metals and types of complexes, as can be shown by the synthesis of [C₅H₅Mn(CO)₂ {NHC(CH₃)₂}], [C₅H₅Fe(CO)₂{NHC(CH₃)₂}]PF₆, [M(CO)₄L₂] (M = Cr, Mo, W; L = (CH₃)₂CNH, C₆H₁₀NH) and [W(CO)₃(diphos){NHC(CH₃)}₂]. Treatment of [Cr(CO)₅NH₃] with urotropine gives [Cr(CO)₅ {N₄(CH₂)₆}] which is also obtained from [Cr(CO)₅THF] and urotropine. The methods of preparation, reactions and spectroscopic properties of the complexes are reported.     

The reaction of amines with phthalimide derivatives a convenient synthesis of isoxazolidine

The reaction of tert-butylamine, isoxazolidine and hydrazine with N-[(3-chloropropyl)oxy]phthalimide is investigated. A convenient synthesis of oxazolidine is described.     

The phase diagram for the binary system K2CrO4CaCrO4

The phase diagram for the binary system K₂CrO₄CaCrO₄ has been determined for CaCrO₄ concentrations up to 60 mole%, using the techniques of differential thermal analysis, X-ray diffraction, and drop calorimetry. Essential features of the phase diagram are: the solid-solid phase transition for pure K₂CrO₄ at 670°C, β-K₂CrO₄ ? α-K₂CrO₄; a eutectoid reaction at 14 mole% CaCrO₄ and 548°C, β-K₂CrO₄ ? α-K₂CrO₄ + K₂CrO₄ · CaCrO₄; a peritectoid event at 50 mole% CaCrO₄ and 640°C, β-K₂CrO₄ + CaCrO₄ ? K₂CrO₄ · CaCrO₄; and a eutectic reaction at 51 mole% CaCrO₄ and 678°C, L ? β-K₂CrO₄ + CaCrO₄. X-ray diffraction studies lead to the determination of the unit cell dimensions for the K₂CrO₄ · CaCrO₄ double salt, a C-centered monoclinic form with a₀ = 7.615(6) Å, b₀ = 22.797(15) Å, c₀ = 9.777(9) Å, β = 115.45(5)°.     

Charge trapping reactions in bilayer electrodes

The cyclic voltammetric peaks for charging trapping and untrapping reactions between the inner and outer redox polymer films of five bilayer electrodes are compared to a theory for control of the rate of charge trapping by electron diffusion rates in the inner polymer film. The five bilayer electrodes use various different redox polymer films (electropolymerized poly-pyridine complexes of Fe, Ru, and Os, and polyvinylferrocene) arranged in different orders. The currents on the rising edge of the bilayer trapping and untrapping peaks follow the electron diffusion theory up to ca. 80% of the peak current; currents thereafter are controlled by another process(es). The analysis yields values for the electron diffusion constants in the inner bilayer polymer films, which agree with one another for different bilayers having the same inner film polymer films and which also agree with independent determinations by other methods. Two of the bilayers are made from the same two polymers, arranged in different inner-outer order. These bilayers also illustrate the occurrence of a “leak reaction”, in which charge trapped in the outer film is discharged via a thermodynamically unfavorable electron transfer reaction with the inner polymer film.     

Synthesis of polymers containing tertiary phosphine oxides using complex bases

Tertiary phosphine oxides have been prepared in excellent yield from primary alkyl halides or aromatic halides and activated sodium phosphinates obtained by reaction of dialkyl phosphine oxides with complex bases (NaNH₂/tBuONa). This reaction has been successfully applied to soluble and cross-linked bromopolystyrenes and to macroporous polystyrenes with bromooctyl substituents giving polymers which contain pendant phosphine oxide groups.     

Further solvent-free reactions of ferrocenylaldehydes: Synthesis of 1,1′-ferrocenyldiimines and ferrocenylacrylonitriles

Grinding of 1,1′-ferrocenedicarboxaldehyde with a 2.2 molar equivalent of an aromatic amine in a solvent-free environment provided excellent yields of 1,1′-ferrocenyldiimines. After mixing the aldehyde and amines, a gum or melt formed which eventually solidified to the product. An analytically pure sample of the product was obtained by cold recrystallization. Grinding of ferrocenecarboxaldehyde and 4-substituted phenylacetonitriles under solvent-free conditions provided good yields of the corresponding ferrocenylacrylonitriles. The yield in this reaction was very low when the substituent group para to the acetonitrile group was electron-donating.