An H2L Schiff-base ligand that was obtained from the monocondensation of diaminomaleonitrile and 4-(diethylamino)salicylaldehyde is reported together with four related nickel(II) complexes formulated as [Ni(L)(L')] (L' = MePhCHNH2, iPrNH2, Py, PPh3). Crystal structures have been solved for H2L, [Ni(L)(MePhCHNH2)], [Ni(L)(iPrNH2)]. Surprisingly, complexation process leads to formation a rather unusual nickel amido (−NH−NiII) bond by deprotonation primary amine H2L. A reduction quadratic...

The coordinating properties of the diaminocarbene (A) and phosphonium ylide (B) ligand types have been investigated systematically through a test family C,C-chelating ligands containing two moieties either kind. overall character o-C6H4A(a)B(b) (a + b = 2) has analyzed from IR CO stretching frequencies isostructural complexes [(eta(2)-C6H4A(a)B(b))Rh(CO)2][TfO]. A NC2H2N(+)(Me)C(-) B Ph2P(+)CH2(-) were first considered. While bearing at least one end (AA, 2 AB, 1) could be generated (and...

Abstract Whereas the external nucleophilic reactivity of α‐amidiniophosphines has been previously illustrated by their complexation to transition‐metal centers, internal electrophilic is herein investigated using BIMIONAP (BIMIONAP=N‐methylated BIMINAP cation, BIMINAP=formal contraction acronyms BIMIP=2,2′‐bis(diphenylphosphino)‐1,1′‐bibenzimidazole and BINAP=2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl). Reaction tetraethylammonium chloride with free found induce heterolytic cleavage N 2 CP...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAqueous ring-opening metathesis polymerization of carboximide-functionalized 7-oxanorbornenesMarc A. Hillmyer, Christine Lepetit, Dominic V. McGrath, Bruce M. Novak, and Robert H. GrubbsCite this: Macromolecules 1992, 25, 13, 3345–3350Publication Date (Print):June 1, 1992Publication History Published online1 May 2002Published inissue 1 June 1992https://pubs.acs.org/doi/10.1021/ma00039a004https://doi.org/10.1021/ma00039a004research-articleACS...

Two copper(II)−gadolinium(III) metal complexes of formula CuIIGdIIILX3 are reported. H2L stands for the Schiff base ligand obtained by condensation 3,4-dimethoxysalicylaldehyde with ethylenediamine (complex 1) or 1R,2R-(+)-1,2-diphenylethylenediamine 2). While 1 reveals a centrosymmetric crystal structure, 2 crystallizes in noncentrosymmetric P212121 space group and exhibits an efficiency 0.3 time that urea second harmonic generation. Due to trend dissociation solution, molecular...

The bulk structure of total and partial carbo-mers graphite, referred to as graphitynes, is investigated by first-principles calculations using the Rutgers–Chalmers nonlocal correlation functional vdW-DF2 in combination with Cooper's exchange C09. This calculation level shown perform well for describing graphene graphite reference structures. AB- ABC-graphityne stackings are predicted be most stable, interlayer distances close one parent. atomic sparsity 2D- 3D-α-graphyne materials resulting...

The coordination chemistry of a potentially pincer-type dicationic meta-phenylene-bis(imidazoliophosphine) ligand 3 to neutral and cationic carbonylrhodium(I) centers has been investigated. Similarly what was observed previously for its ortho-phenylene counterpart, found bind the RhCl(CO) fragment in trans-chelating manner that makes possible weak Rh-C(H) interaction, inferred from nonbonding but relatively short Rh-C Rh-H contacts solid state structure adduct (3)RhCl(CO) (5). Formation...

The missing entry, namely, the "C-anagostic" or η(1)-C interaction, closing agostic-anagostic series of metal-CH(aryl) interactions is found in a bis(amidiniophosphine) P(CH)P pincer rhodium complex. three entries, agostic η(2)-(C,H), anagostic (related to hydrogen bonding, thus recoined here as "H-anagostic"), and C-anagostic interactions, are unambiguously characterized by electron localization function (ELF) topological analysis. Other theoretical tools such noncovalent interaction (NCI)...

The aromaticity and homoaromaticity in ring carbomers of [N]annulenes [N]cycloalkanes (i.e., [N]pericyclynes) are investigated using the topological analysis electron localization function (ELF). In a qualitative viewpoint, ELF picture carbo[N]annulenes is systematically "expanded" with respect to those parent [N]annulenes. allows us evaluate weight various resonance forms corresponding (i) out-of-plane cyclic π delocalization (ii) in-plane homodelocalization. latter also quantified for...

A series of 10 (2−11) new chiral (salicylaldiminato)tin Schiff base complexes obtained from the condensation 4-(diethylamino)salicylaldehyde and various amino acids, in presence diphenyltin oxide, is reported together with parent achiral (1) derivative. Compounds 2−7 crystallize P212121 orthorhombic space group, their quadratic nonlinear optical properties are investigated. At molecular level, derivatives possess similar electronic spectra (λmax ≈ 395 nm), hence hyperpolarizabilities (β),...

The influence of the formal electrostatic interaction on cis/trans coordination mode at a PdCl(2) center is investigated in family isostructural flexible diphosphine ligands Ph(2)P-X-C(6)H(4)-Y-PPh(2), where X and Y stand for neutral or cationic N,C-imidazolylene linkers. While monocationic spontaneously behave as classical cis-chelating ligands, only dicationic diphosphine, repulsion between positive charges specifically takes place, observed to trans-chelating ligand. crucial role...

The coordination of Ni2+ ions to lattice oxygens in calcined X and Y zeolites has been extensively studied. A survey the literature is presented here. From X-ray diffraction, are known occupy preferentially hexagonal prisms (SI) octahedral symmetry. main d−d absorption bands NiX NiY were assigned on this basis. corresponding low value crystal field (10Dq ≈ 6400 cm-1) was accounted for by unusual long Ni−O bond lengths at SI sites. We demonstrate here that assignment not consistent with...

Geometries and bonding energies have been calculated at the B3LYP/3-21G** B3LYP/DZVP2 levels in a series of [M(η6-C6H6)]n+ complexes where M = Ti, Cr, Co (n 0), V 3), Fe 0, 2), Ni 2, 4), Cu 1) with C6v or near symmetry. Metal−benzene is discussed on basis MO perturbation schemes. A correlation between total benzene charge frequency shift E1 ring vibration (experimentally 1483 cm-1 for isolated benzene) evidenced, allowing interpretation experimental data.

Abstract The configurational stability of biaryl motifs is addressed for the 1‐naphthyl‐ N ‐benzimidazolyl motif substituted by a single diphenylphosphinyl group at 2‐position. atropoenantiomers N‐methylated cation H‐MIOP, less sterically locked analogue neutral H‐MOP ligand, were resolved enantiospecific cleavage 2 CP bond enantiomers BIMIONAP. latter obtained N‐methylation previously BIMINAP. PdCl complexes P,C‐chelating ‐heterocyclic carbene (NHC)–phosphine ligands derived from ( R )‐...

When targeting the quadrupolar p-dianisyltetraphenyl-carbo-benzene by reductive treatment of a hexaoxy-[6]pericyclyne precursor 3 with SnCl(2)/HCl, strict control conditions allowed for isolation three C(18)-macrocyclic products: targeted aromatic carbo-benzene 1, sub-reduced non-aromatic carbo-cyclohexadiene 4A, and an over-reduced dihydro-carbo-benzene 5A. Each them was fully characterized its absorption NMR spectra, which were interpreted comparison calculated spectra from static...

Compounds featuring bonds between mercury and transition metals are of interest for their intriguing/ambiguous bonding scarcely explored reactivities. We report herein the synthesis reactivities new compound [(POCOP)Ni]2Hg, [Ni2Hg], a trinuclear Ni–Hg–Ni core (POCOP = κP,κC,κP´‐2,6‐(i‐Pr2PO)2C6H3). [Ni2Hg] reacts with CO2 to give carbonate‐bridged complex [Ni2CO3]. Bubbling CO gas through solution [Ni2CO3] gave its μ−CO2 analogue [Ni2CO2], which itself back [Ni2CO3], indicating that these...

Compounds featuring bonds between mercury and transition metals are of interest for their intriguing/ambiguous bonding scarcely explored reactivities. We report herein the synthesis reactivities new compound [(POCOP)Ni]2Hg, [Ni2Hg], a trinuclear Ni–Hg–Ni core (POCOP = κP,κC,κP´‐2,6‐(i‐Pr2PO)2C6H3). [Ni2Hg] reacts with CO2 to give carbonate‐bridged complex [Ni2CO3]. Bubbling CO gas through solution [Ni2CO3] gave its μ−CO2 analogue [Ni2CO2], which itself back [Ni2CO3], indicating that these...