A new 2-carboxylate-substituted 4,4'-bipyridine ligand: coordination chemistry of 4,4'-bipyridine-2-carboxylic acid and its synthetic intermediate 2-methyl-4,4'-bipyridine

The first monocarboxylate-substituted 4,4'-bipyridine ligand, 4,4'-bipyridine-2-carboxylic acid (4-(pyridin-4-yl)pyridine-2-carboxylic acid (PPCAH)), has been successfully synthesized from 4,4'-bipyridine. Reactions with transition metals zinc and manganese were used to establish the coordination characteristics of the product, 4,4'-bipyridine-2-carboxylic acid, and of the synthetic intermediate, 2-methyl-4,4'-bipyridine, by single-crystal X-ray diffraction. The ligand PPCAH is useful for the formation of metal-containing building blocks that can be used in the assembly of mixed-metal framework materials. The synthesis and structure of one such mixed-metal coordination polymer, Cu(PPCA)(2)HgI(2), is also presented.     

Semigroup identities in the monoid of two-by-two tropical matrices

We show that the monoid $M_{2}(\mathbb {T})$ of 2×2 tropical matrices is a regular semigroup satisfying the semigroup identity $$A^2B^4A^2A^2B^2A^2B^4A^2=A^2B^4A^2B^2A^2A^2B^4A^2.$$ Studying reduced identities for subsemigroups of $M_{2}(\mathbb {T})$ , and introducing a faithful semigroup representation for the bicyclic monoid by 2×2 tropical matrices, we reprove Adjan’s identity for the bicyclic monoid in a much simpler way.     

Monoid Valuations and Value Ordered Supervaluations

We complement two papers on supertropical valuation theory ([11 Izhakian , Z. , Knebusch , M. , Rowen , L. ( 2011 ). Supertropical semirings and supervaluations . J. Pure and Applied Alg. 215 ( 10 ): 2431 – 2463 . Preprint at arXiv:1003.1101 .[Crossref], [Web of Science ®] , [Google Scholar]], [12 Izhakian , Z. , Knebusch , M. , Rowen , L. ( 2013 ). Dominance and transmissions in supertropical valuation theory . Commun. Algebra 41 ( 7 ): 2736 – 2782 .[Taylor &; Francis Online], [Web of Science ®] , [Google Scholar]]) by providing natural examples of m-valuations (= monoid valuations), and afterwards of supervaluations and transmissions between them. These supervaluations have values in totally ordered supertropical semirings, and the transmissions discussed respect the orderings. We develop the basics of the theory of such semirings and transmissions.     

Ylide‐Functionalized Phosphines: Strong Donor Ligands for Homogeneous Catalysis

Phosphines are important ligands in homogenous catalysis and have been crucial for many advances, such as in cross‐coupling, hydrofunctionalization, or hydrogenation reactions. Herein we report the synthesis and application of a novel class of phosphines bearing ylide substituents. These phosphines are easily accessible via different synthetic routes from commercially available starting materials. Owing to the extra donation from the ylide group to the phosphorus center the ligands are unusually electron‐rich and can thus function as strong electron donors. The donor capacity surpasses that of commonly used phosphines and carbenes and can easily be tuned by changing the substitution pattern at the ylidic carbon atom. The huge potential of ylide‐functionalized phosphines in catalysis is demonstrated by their use in gold catalysis. Excellent performance at low catalyst loadings under mild reaction conditions is thus seen in different types of transformations.     

Pressure induced octahedral tilting distortion in Ba2YTaO6

Herein we communicate the first example of a pressure induced octahedral tilting distortion in a double perovskite phase, which was observed during the structural characterization of Ba2YTaO6 using high-pressure synchrotron X-ray powder diffraction.     

Single-crystal structure of the 2H-related perovskites (A(3-x)Nax)NaBO6 (A = La, Pr, Nd; B = Rh, Pt)

Single crystals of La(2.47)Na(1.53)RhO6, Pr(2.45)Na(1.55)RhO6, Nd(2.45)Na(1.55)RhO6, La2Na2PtO6, and Nd2Na2PtO6 were grown from carbonate and "wet" hydroxide fluxes. All were found to crystallize in the trigonal space group R3c and adopt the K4CdCl6 structure.     

Decompositions of modules lacking zero sums

A module over a semiring lacks zero sums (LZS) if it has the property that v +w = 0 implies v = 0 and w = 0. While modules over a ring never lack zero sums, this property always holds for modules over an idempotent semiring and related semirings, so arises for example in tropical mathematics.A direct sum decomposition theory is developed for direct summands (and complements) of LZS modules: The direct complement is unique, and the decomposition is unique up to refinement. Thus, every finitely generated “strongly projective” module is a finite direct sum of summands of R (assuming the mild assumption that 1 is a finite sum of orthogonal primitive idempotents of R). This leads to an analog of the socle of “upper bound” modules. Some of the results are presented more generally for weak complements and semi-complements. We conclude by examining the obstruction to the “upper bound” property in this context.     

Tropical matrix groups

We study the structure of groups of finitary tropical matrices under multiplication. We show that the maximal groups of \(n \times n\) tropical matrices are precisely the groups of the form \(G \times \mathbb {R}\) where G is a group admitting a 2-closed permutation representation on n points. Each such maximal group is also naturally isomorphic to the full linear automorphism group of a related tropical polytope. Our results have numerous corollaries, including the fact that every automorphism of a projective (as a module) tropical polytope of full rank extends to an automorphism of the containing space.     

The solid-state structure of (+)-(i)-menthyl 2-formamido-4, 4,4-trifluorobutanoate and the hydrogenation of the 2-butenoate precursor

Hydrogenation ofZ-(–)-(1R, 3R, 4S)-menthyl 2-formamido-4,4,4-trifluoro-2-butenoate catalyzed by Pd/C was performed at atmospheric pressure to yield a mixture of (2R, 1R, 3R, 4S)- and (2S, 1R, 3R, 4S)-menthyl 2-formamido-4,4,4-trifluorobutanoate diastereomers in a 5545 ratio, respectively. Repeated fractional crystallization from ethyl acetate and vapor diffusion of petroleum ether afforded (+)–(2S, 1R, 3R, 4S)-menthyl 2-formamido-4,4,4-trifluorobutanoate as clear colorless, crystalline prisms which were subjected to single-crystal X-ray diffraction analysis. The crystals belong to the orthorhombic system P2₁2₁2₁, and at 213 K:a=5.054(1),b= 10.000(2),c=32.707(1) Å,V=1652.9(4) ų,Z=4,R(F)=0.040, andR _w (F)=0.037. The finding of the (2S)-configuration for the formamido-acid portion of the (+)-ester enabled the configurational assignment of the asymmetric hydrogenation products ofZ-methyl 2-formamido-4, 4,4-trifluoro-2-butenoate catalyzed by chiral diphosphine/rhodium(I) complexes.