Oxidative Addition of Disulfides, Alkyl Sulfides, and Diphosphides to an Aluminum(I) Center.

The aluminum(I) compound NacNacAl (1) reacts with diphenyl disulfide and diethyl sulfide to form the respective four-coordinate bis(phenyl sulfide) complex NacNacAl(SPh)2 (2) and alkyl thiolate aluminum complex NacNacAlEt(SEt) (3). As well, reaction of 1 with tetraphenyl diphosphine furnishes the bis(diphenyl phosphido) complex NacNacAl(PPh2)2 (4). Production of 3 and 4 are the first examples of C(sp(3))-S and R2P-PR2 activation by a main-group element complex.

Hydridosilylamido complexes of Ta and Mo isolobal with Berry's zirconocenes: syntheses, β-Si-H agostic interactions, catalytic hydrosilylation, and insight into mechanism.

The syntheses of novel Group 5 and Group 6 hydrosilylamido complexes of the type R(ArN[double bond, length as m-dash])M{N((t)Bu)SiMe2-H}X (M = Ta, R = Cp; M = Mo, R = ArN; X = Cl, H, OBn, Me) are described. The various substituents in the X position seem to play the key role in determining the extent of β-agostic interaction with the Si-H bond. The Mo agostic hydrido complex (ArN[double bond, length as m-dash])2Mo{η(3)-N((t)Bu)SiMe2-H}H is a pre-catalyst for the hydrosilylation of carbonyls.

Supramolecular Dimerization and [2 + 2] Photocycloaddition Reactions of Crown Ether Styryl Dyes Containing a Tethered Ammonium Group: Structure-Property Relationships.

Molecular self-assembly is an effective strategy for controlling the [2 + 2] photocycloaddition reaction of olefins. The geometrical properties of supramolecular assemblies are proven to have a critical effect on the efficiency and selectivity of this photoreaction both in the solid state and in solution, but the role of other factors remains poorly understood. Convenient supramolecular systems to study the structure-property relationships are pseudocyclic dimers spontaneously formed by styryl dyes containing a crown ether moiety and a remote ammonium group.

Menthols as Chiral Auxiliaries for Asymmetric Cycloadditive Oligomerization: Syntheses and Studies of β-Proline Hexamers.

To produce a novel class of structurally ordered poly-β-prolines, an emergent method for synthesizing chiral β-peptide molecular frameworks was developed based on 1,3-dipolar cycloaddition chemistry of azomethine ylides. Functionalized short β-peptides with up to six monomeric residues were efficiently synthesized in homochiral forms using a cycloadditive oligomerization approach. X-ray, NMR, and CD structural analyses of the novel β-peptides revealed secondary structure features that were generated primarily by Z/E-β-peptide bond isomerism.

NHC carbene supported half-sandwich hydridosilyl complexes of ruthenium: the impact of supporting ligands on Si∙∙∙H interligand interactions.

Reaction of complex [CpRu(pyr)3][PF6] (3) with the NHC carbene IPr (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) results in the NHC complex [Cp(IPr)Ru(pyr)2][PF6] (4), which was studied by NMR specroscopy and X-ray diffraction analysis. Reaction of [Cp(IPr)Ru(pyr)2][PF6] (4) with LiAlH4 leads to the trihydride Cp(IPr)RuH3 (5) characterised by spectroscopic methods. Heating compound 5 with hydrosilanes gives the dihydrido silyl derivatives Cp(IPr)RuH2(SiR3) (6).

Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations.

A series of cross-conjugated compounds based on an (E)-4,4'-(hexa-3-en-1,5-diyne-3,4-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) skeleton (1-6) have been synthesized. The linear optical absorption properties can be tuned by modification of the substituents at the 1 and 5 positions of the hexa-3-en-1,5-diynyl backbone (1: Si(CH(CH3)2)3, 2: C6H4C≡CSi(CH3)3, 3: C6H4COOCH3, 4: C6H4CF3, 5: C6H4C≡N, 6: C6H4C≡CC5H4N), although attempts to introduce electron-donating (C6H4CH3, C6H4OCH3, C6H4Si(CH3)3) substituents at these positions were hampered by the ensuing decreased stability of the compounds. Spectroelectrochemical investigations of selected examples, supported by DFT-based computational studies, have shown that one- and two-electron oxidation of the 1,2-bis(triarylamine)ethene fragment also results in electronic changes to the perpendicular π-system in the hexa-3-en-1,5-diynyl branch of the molecule.

Syntheses, structural characterisation and electronic structures of some simple acyclic amino carbene complexes.

Reactions of the vinylidene complexes [M([double bond, length as m-dash]C[double bond, length as m-dash]CH2)(PP)Cp']PF6 with NH3 readily afford the acyclic amino carbene complexes [M{C(Me)NH2}(PP)Cp']PF6 [M(PP)Cp' = Fe(dppe)Cp, Ru(dppe)Cp, Ru(PPh3)2Cp, Ru(dppe)Cp*]. Crystallographic, spectroscopic and computational data support a description of these complexes in terms of a M-{C(Me)[double bond, length as m-dash]N(+)H2} mesomeric form, and simple σ-coordination of the singlet acyclic amino carbene.

Crystal structure of 3-bromo-methyl-2-chloro-6-(di-bromo-meth-yl)quinoline.

In the title compound, C11H7Br3ClN, the quinoline ring system is approximately planar (r.m.s.

The anatomy of a comprehensive constrained, restrained refinement program for the modern computing environment - Olex2 dissected.

This paper describes the mathematical basis for olex2.refine, the new refinement engine which is integrated within the Olex2 program. Precise and clear equations are provided for every computation performed by this engine, including structure factors and their derivatives, constraints, restraints and twinning; a general overview is also given of the different components of the engine and their relation to each other.

Synthesis, structure, and properties of supramolecular photoswitches based on ammonioalkyl derivatives of crown ether styryl dyes.

The synthesis of new styryl dyes derived from 4-pyridine and 4-quinoline and having an ammonioalkyl N-substituent and benzocrown ether moieties of different sizes and with different sets of heteroatoms was developed. Spontaneous "head-to-tail" dimerization of these dyes via the formation of numerous hydrogen bonds between the terminal NH3(+) groups and crown ether moieties was detected in MeCN solutions. The stability constants of the dimeric complexes having pseudocyclic structure were studied by (1)H NMR titration.

Insights into the crystallisation process from anhydrous, hydrated and solvated crystal forms of diatrizoic acid.

Diatrizoic acid (DTA), a clinically used X-ray contrast agent, crystallises in two hydrated, three anhydrous and nine solvated solid forms, all of which have been characterised by X-ray crystallography. Single-crystal neutron structures of DTA dihydrate and monosodium DTA tetrahydrate have been determined. All of the solid-state structures have been analysed using partial atomic charges and hardness algorithm (PACHA) calculations.

Fluorotetrahydroquinolines from diethyl 2-fluoromalonate ester.

A short series of fluorotetrahydroquinolines was synthesised in two steps from diethyl fluoromalonate and appropriate ortho-nitrobenzyl bromide precursors.

Experimental and theoretical studies of quadrupolar oligothiophene-cored chromophores containing dimesitylboryl moieties as π-accepting end-groups: syntheses, structures, fluorescence, and one- and two-photon absorption.

Quadrupolar oligothiophene chromophores composed of four to five thiophene rings with two terminal (E)-dimesitylborylvinyl groups (4 V-5 V), and five thiophene rings with two terminal aryldimesitylboryl groups (5 B), as well as an analogue of 5 V with a central EDOT ring (5 VE), have been synthesized via Pd-catalyzed cross-coupling reactions in high yields (66-89%). Crystal structures of 4 V, 5 B, bithiophene 2 V, and five thiophene-derived intermediates are reported. Chromophores 4 V, 5 V, 5 B and 5 VE have photoluminescence quantum yields of 0.

Syntheses of fluorooxindole and 2-fluoro-2-arylacetic acid derivatives from diethyl 2-fluoromalonate ester.

Diethyl 2-fluoromalonate ester is utilised as a building block for the synthesis of 2-fluoro-2-arylacetic acid and fluorooxindole derivatives by a strategy involving nucleophilic aromatic substitution reactions with ortho-fluoronitrobenzene substrates followed by decarboxylation, esterification and reductive cyclisation processes.

Multiple coupling of silanes with imido complexes of Mo.

The bis(imido) complexes ((t)BuN[double bond, length as m-dash])2Mo(PMe3)(L) (L = PMe3, C2H4) react with up to three equivalents of silane PhSiH3 to give the imido-bridged disilyl silyl Mo(vi) complex ((t)BuN){μ-(t)BuN(SiHPh)2}Mo(H)(SiH2Ph)(PMe3)2 (3) studied by NMR, IR and X-ray diffraction. NMR data supported by DFT calculations show that complex 3 is an unusual example of a silyl hydride of Mo(VI), without significant SiH interaction. Mechanistic NMR studies revealed that silane addition proceeds in a stepwise manner via a series of Si-H∙∙∙M agostic and silanimine complexes whose structures were further elucidated by DFT calculations.

Structure of organic solids at low temperature and high pressure.

This tutorial review looks at structural and supramolecular chemistry of molecular solids under extreme conditions, and introduces the instrumentation and facilities that enable single crystal diffraction studies on molecular crystals at both high pressure and low temperature. The equipment used for crystallography under extreme conditions is explored, particularly pressure cells such as the diamond anvil cell, and their mechanism of action, as well as the cryogenic apparatus which allows materials to be cooled to significantly low temperatures. The review also covers recent advances in the structural chemistry of molecular solids under extreme conditions with an emphasis on the use of single crystal crystallography in high pressure and low temperature environments to probe polymorphism and supramolecular interactions.

Regiospecific formation and unusual optical properties of 2,5-bis(arylethynyl)rhodacyclopentadienes: a new class of luminescent organometallics.

A series of 2,5-bis(arylethynyl)rhodacyclopentadienes has been prepared by a rare example of regiospecific reductive coupling of 1,4-(p-R-phenyl)-1,3-butadiynes (R=H, Me, OMe, SMe, NMe2, CF3, CO2Me, CN, NO2, -C≡C-(p-C6H4-NHex2), -C≡C-(p-C6H4-CO2Oct)) at [RhX(PMe3)4] (1) (X=-C≡C-SiMe3 (a), -C≡C-(p-C6H4-NMe2) (b), -C≡C-C≡C-(p-C6H4-NPh2) (c) or -C≡C-{p-C6H4-C≡C-(p-C6H4 -N(C6H13)2)} (d) or Me (e)), giving the 2,5-bis(arylethynyl) isomer exclusively. The rhodacyclopentadienes bearing a methyl ligand in the equatorial plane (compound 1 e) have been converted into their chloro analogues by reaction with HCl etherate. The rhodacycles thus obtained are stable to air and moisture in the solid state and the acceptor-substituted compounds are even stable to air and moisture in solution.

Cutting-edge techniques used for the structural investigation of single crystals.

X-ray crystallography has become the leading technique for studying the structure of matter at the atomic and molecular level. Today it underpins all sciences and is widely applied in industry. It is essential in the development of new materials.

A combined computational and spectroelectrochemical study of platinum-bridged bis-triarylamine systems.

The character of the electronic transitions in the ultraviolet-visible-near infrared (UV-vis-NIR) spectra of platinum-bis(alkynyl) bridged, bis-triarylamine mixed-valence systems trans-[Pt(C≡CC6H4NAr2)2 (PR3)2](n+) (R = ethyl, Ar = C6H4CH3-4 (1) or C6H4OCH3-4 (2); R = Ph, Ar = C6H4CH3-4 (3) or C6H4OCH3-4 (4), n = 0, 1, 2) has been determined from a combination of spectroscopic measurement and density functional theory calculations. The hybrid functional BLYP35 in combination with a suitable solvent model (i.e.

Synthesis, structure, and characterization of chromo(fluoro)ionophores with cation-triggered emission based on N-methylaza-crown-ether styryl dyes.

Novel 2-benzothiazole-, 4-pyridine-, and 2- and 4-quinoline-based styryl dyes containing an N-methylbenzoaza-15(18)-crown-5(6)-ether moiety were synthesized. A detailed electronic spectroscopy study revealed high performance of these compounds as optical molecular sensors for alkali and alkaline-earth metal cations. They were shown to considerably surpass analogous chromoionophores based on N-phenylaza-crown ethers regarding both the ionochromism and the cation-binding ability.

Refining the interpretation of near-infrared band shapes in a polyynediyl molecular wire.

Spinning to improve (band) shape: A blend of theoretical and experimental work demonstrates that the rotational conformation of mixed-valence complexes influences the low-energy (NIR) transitions in such molecules. Interpretations of the NIR band shapes are presented.

Multimetastability in a spin-crossover compound leading to different high-spin-to-low-spin relaxation dynamics.

The relaxation kinetics of both the thermally trapped and photoinduced high-spin (HS) states of the spin-crossover compound [Fe(H4L)2](ClO4)2·H2O·2(CH3)2CO (1) were measured and found to differ significantly. Calorimetry measurements then demonstrated that relaxation of the thermally trapped phase was concurrent with two separate processes, not previously detected as such. Determination of the photogenerated HS structure revealed a new metastable HS state of the system, much closer structurally to the low-spin phase than the thermally trapped one.

Unusual structure, fluxionality, and reaction mechanism of carbonyl hydrosilylation by silyl hydride complex [(ArN=)Mo(H)(SiH2Ph)(PMe3)3].

The reactions of bis(borohydride) complexes [(RN=)Mo(BH4)2(PMe3)2] (4: R = 2,6-Me2C6H3; 5: R = 2,6-iPr2C6H3) with hydrosilanes afford new silyl hydride derivatives [(RN=)Mo(H)(SiR'3)(PMe3)3] (3: R = Ar, R'3 = H2Ph; 8: R = Ar', R'3 = H2Ph; 9: R = Ar, R'3 = (OEt)3; 10: R = Ar, R'3 = HMePh). These compounds can also be conveniently prepared by reacting [(RN=)Mo(H)(Cl)(PMe3)3] with one equivalent of LiBH4 in the presence of a silane. Complex 3 undergoes intramolecular and intermolecular phosphine exchange, as well as exchange between the silyl ligand and the free silane.

The formation of peroxide degradation products of photochromic triphenylimidazolyl radical-dimers.

Following the recent report of Abe and co-workers (Phys. Chem. Chem.

trans-Bis[1,2-bis-(diphenyl-phosphan-yl)ethane]-chlorido(ethyn-yl)ruthenium(II).

The mol-ecular structure of the title compound, trans-[Cu(C2H)Cl(C26H24P2)2], consists of an Ru(II) cation, located on an inversion centre, in an octa-hedral environment defined by two chelating phosphines, one acetyl-ide and one chloride ligand. The -C CH and the chlorine ligands are disordered over two equivalent positions (0.5 occupancy each).