Triangular Ni2Ln and Ni2Y complexes derived from di-2-pyridyl ketone: Synthesis, structures and magnetic properties

The synthetic investigation of the Ni^II/M(NO₃)₃·6H₂O/di-2-pyridyl ketone [(py)₂CO] tertiary reaction system in EtOH has yielded triangular Ni₂M cationic complexes (M = lanthanide, Y). The reaction between Ln(NO₃)₃·6H₂O, Ni(ClO₄)₂·6H₂O, (py)₂CO and base (1:3:3:3) in EtOH under gentle heating gave the isostructural complexes [Ni₂Ln{(py)₂C(OEt)(O)}₃{(py)₂C(OH)(O)}(NO₃)(H₂O)](ClO₄)₂ (Ln = Gd, 2; Ln = Tb, 3) in high yields. The ligands (py)₂C(OEt)(O)⁻ and (py)₂C(OH)(O)⁻ are the monoanions of the hemiketal and gem-diol derivatives of (py)₂CO, respectively, formed in situ in the presence of the metal ions. The cations of 2 and 3 consist of one 8-coordinate Ln^III and two distorted octahedral Ni^II atoms in an essentially isosceles, triangular arrangement capped by a central μ₃-Ο⁻ atom of the unique 3.3011 (Harris notation) (py)₂C(OH)(O)⁻ ligand. Each metal-metal edge is bridged by the deprotonated O atom of one 2.2011 (py)₂C(OEt)(O)⁻ ligand. The isostructural complexes [Ni₂M{(py)₂C(OEt)(O)}₄(NO₃)(H₂O)]₂[M(NO₃)₅](ClO₄)₂ (M = Y, 4 ; M = Tb, 5 ; M = Dy, 6) were prepared by the 1:1 reaction of the mononuclear “metalloligand” [Ni(O₂CMe){(py)₂CO}{(py)₂C(OH)₂}](ClO₄) (1) and M(NO₃)₃·6H₂O in EtOH under mild heating in moderate to good yields. The structures of the dications of 4-6 are similar to those in 2 and 3, the only difference being the replacement of the unique 3.3011 (py)₂C(OH)(O)⁻ ligand of the latter by one 3.3011 (py)₂C(OEt)(O)⁻ group in the former. The Y^III, Tb^III and Dy^III atoms in [M(NO₃)₅]²⁻ are coordinated by five bidentate chelating nitrato groups. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the ligands. Variable temperature, solid-state direct current magnetic susceptibility and magnetization studies were carried out on dried samples of 2-4. The data indicate ferromagnetic Ni?Ni and Ni?Gd exchange interactions, and an S_T = 11/2 ground state for 2. Complex 3 is characterized by a high-spin ground state while the ferromagnetic Ni?Ni interaction for 2 is independently supported by the study of 4. No out-of-phase, alternating current susceptibility signals have been detected for 3 that would be indicative of SMM behavior.     

Highly enantioselective and regioselective copper-catalyzed 1,4 addition of grignard reagents to cyclic enynones

In this letter we describe an unusual result in terms of regioselectivity with respect to copper-catalyzed conjugate additions of various Grignard reagents to cyclic enynones. The use of Cu(OTf)(2) and NHC ligand L1 as the catalyst combination in CH(2)Cl(2) led to the unique formation of the 1,4 adduct. This selectivity does not follow the general trend previously observed in the literature using extended Michael acceptors. Moreover these reactions allowed for the creation of a quarternary stereogenic center with enantioselectivities up to 97% ee.     

Organocuivreux vinyliques : IX. Addition de derives organiques du cuivre sur l'acetylene

The addition of various alkylcopper derivatives to acetylene is described. The best reagents are lithium dialkylcuprates in ether which form Z-dialkenylcuprates. ω-Funtionalized dialkylcuprates also add cleanly to acetylene. The Z-dialkenylcuprates thus obtained are iodinated to afford stereospecifically Z-1-iodoalkenes.     

Chiral phosphorus ligands for the asymmetric conjugate addition of organocopper reagents

The asymmetric conjugate addition of medium order alkyl cuprate reagents. R₅Cu₃Li₂, to 2-cyclohexen-1-one. 2-cyclopenten-1-one and 2-cyctohepten-1-one, with the help of phosphorus ligand B^*, is described. 3-Alkyl substituted cyclohexanones are obtained in essentially optically pure form. The same chiral ligand, associated with CuI, in catalylic amount (10%), allows the asymmetric conjugate addition of Et₂Zn to 2-cyclohexen-1-one.     

Structure determination of oligomeric alkannin and shikonin derivatives

Monomeric alkannin and shikonin (A/S) are potent pharmaceutical substances with a wide spectrum of biological activity and comprise the active ingredients for several pharmaceutical preparations. Therefore, the determination of the impurities, degradation products or byproducts in alkannin and shikonin samples is of great importance. Oligomeric alkannin and shikonin are formed during biosynthesis of these bioactive secondary metabolites in Boraginaceaous root plants, during tissue culture production of A/S, during alkaline hydrolysis of A/S esters and also thermal treatment of A/S. In the present study, a dimeric alkannin/shikonin compound was isolated by size exclusion chromatography from alkannin and shikonin commercial samples and its structure was determined by one- and two-dimensional NMR spectroscopy. The structure of the most abundant oligomeric species in these samples, a dimeric naphthoquinone, was established for the fi rst time, indicating that coupling of the side chain of one naphthoquinone unit with the aromatic ring of a second naphthoquinone leads to dimer formation. This type of coupling allows further oligomerization by leaving one isohexenyl side chain available at the second monomer unit.     

Subplanes of projective planes of order 121

We determine orbit representatives of all proper subplanes generated by quadrangles of a Veblen-Wedderburn (VW) plane Π of order 11² and the Hughes plane Σ of order 11² under their full collineation groups. In Π, there are 13 orbits of Baer subplanes all of which are desarguesian and approximately 3000 orbits of Fano subplanes. In Σ, there are 8 orbits of Baer subplanes all of which are desarguesian, 2 orbits of subplanes of order 3 and at most 408,075 distinct Fano subplanes. This work was motivated by the well-known question: “Does there exist a non-desarguesian projective plane of prime order?” The question remains unsettled.     

Minimal logarithmic signatures for finite groups of Lie type

A logarithmic signature (LS) for a finite group G is an ordered tuple α =  [A ₁, A ₂, . . . , A _n ] of subsets A _i of G, such that every element ${g \in G}$ can be expressed uniquely as a product g =  a ₁ a ₂ . . . a _n , where ${a_i \in A_i}$ . The length of an LS α is defined to be ${l(\alpha)= \sum^{n}_{i=1}|A_i|}$ . It can be easily seen that for a group G of order ${\prod^k_{j=1}{p_j}^{m_j}}$ , the length of any LS α for G, satisfies, ${l(\alpha) \geq \sum^k_{j=1}m_jp_j}$ . An LS for which this lower bound is achieved is called a minimal logarithmic signature (MLS) (González Vasco et al., Tatra Mt. Math. Publ. 25:2337, 2002). The MLS conjecture states that every finite simple group has an MLS. This paper addresses the MLS conjecture for classical groups of Lie type and is shown to be true for the families PSL _n (q) and PSp _2n (q). Our methods use Singer subgroups and the Levi decomposition of parabolic subgroups for these groups.     

On the use of phosphoramidite ligands in copper-catalyzed asymmetric transformations with trialkylaluminum reagents

[reaction: see text] Phosphoramidites based on BINOL readily react with trimethylaluminum in "noncoordinating" solvents, leading to the corresponding aminophosphine which is the real ligand in copper-catalyzed asymmetric transformations. This artifact explains the experimental differences in the asymmetric ring opening of meso bicyclic hydrazines using dialkylzinc or trialkylaluminum reagents as nucleophiles.     

Synthesis and characterization of chiral poly(alkyl isocyanates) by coordination polymerization using a chiral half‐titanocene complex

A new chiral half‐titanocene complex, [CpTiCl₂(O‐(S)?2‐Bu)], is synthesized and characterized by ¹H and ¹³C NMR spectroscopy. This complex is employed for the coordination polymerization of n‐butyl and n‐hexyl‐ isocyanate leading to chiral polymers, as revealed by their CD spectra. Only the left‐handed helix is produced, due to the chiral (S)?2‐butoxy group, which is bound to the polymer chain end. The polymerization of 3‐(triethoxysilyl)propyl isocyanate produces less soluble polymers. On the other hand, phenyl isocyanate reacts slowly with the complex leading quantitatively and selectively to triphenyl isocyanurate. 2‐Ethylhexyl isocyanate is slowly and selectively cyclotrimerized in the presence of the half‐titanocene complex. However, a statistical copolymer of 2‐ethylhexyl isocyanate and hexyl isocyanate is produced. The reaction of benzyl isocyanate with the complex leads to a mixture of low molecular weight polymer and cyclotrimer. The polymers are characterized using SEC, NMR, and CD spectroscopy and their thermal properties are investigated by TGA/DSC analysis. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2141–2151