Facile Access to Organostibines via Selective Organic Superbase Catalyzed Antimony-Carbon Protonolysis.

The selective formation of antimony-carbon bonds via organic superbase catalysis under metal- and salt-free conditions is reported. This novel approach utilizes electron-deficient stibine, Sb(C6F5)3, to give upon base-catalyzed reactions with weakly acidic aromatic and heteroaromatic hydrocarbons access to a range of new aromatic and heteroaromatic stibines, respectively, with loss of C6HF5. Also, the significantly less electron-deficient stibines, Ph2SbC6F5 and PhSb(C6F5)2 smoothly underwent base-catalyzed exchange reactions with a range of terminal alkynes to generate the stibines of formulae PhSb(C≡CPh)2, and Ph2SbC≡CR [R=C6H5, C6H4-NO2, COOEt, CH2Cl, CH2NEt2, CH2OSiMe3, Sb(C6H5)2], respectively. These formal substitution reactions proceed with high selectivity as only the C6F5 groups serve as a leaving group to be liberated as C6HF5 upon formal proton transfer from the alkyne. Kinetic studies of the base-catalyzed reaction of Ph2SbC6F5 with phenyl acetylene to form Ph2SbC≡CPh and C6HF5 suggested the empirical rate law to exhibit a first-order dependence with respect to the base catalyst, alkyne and stibine. DFT calculations support a pathway proceeding via a concerted σ-bond metathesis transition state, where the base catalyst activates the Sb-C6F5 bond sequence through secondary bond interactions.

Characterization of Water Structure and Phase Behavior within Metal-Organic Nanotubes.

Water behavior under nanoconfinement varies significantly from that in the bulk but also depends on the nature of the pore walls. Hybrid compound offers the ideal system to explore water behavior in complex materials, so a model metal-organic nanotube (UMONT) material was utilized to explore the behavior of water between 100 and 293 K. Single-crystal X-ray and neutron diffraction revealed the formation of a filled Ice-I arrangement that was previously predicted to only occur under high pressures. 17O NMR spectra suggest that the onset of melting for the water in the UMONT channels occurs at 98 K and the presence of ice-like water up to 293 K, indicating that the complete ice-water transition does not occur before dehydration of the material. Overall, the water behavior differs significantly from hydrophobic single-walled carbon nanotubes indicating precise control over water can be achieved through rational design of hybrid materials.

Cerium(IV) Pyrasal Complexes: A pH-Dependent 8- to 10-Coordinate Cerium Chelate Switch.

In this work, five cerium(IV) complexes were synthesized, three of which were structural isomorphs from the same pyrasal ligand with the solid-state result identified by structural analysis dependent on the initial pH of the reaction solution and the temperature at which the reaction is performed. The ligands explored here are pyrasal ligands, which are Schiff-base ligands formed by the condensation of 2,3-diaminopyrazine and a salicylaldehyde derivative. Pyrasal ligands have weaker binding than other salophen-type ligands due to the electron-withdrawing effect of the nitrogen atoms contained within the pyrazine ring. The weaker binding leaves the ligand more susceptible to the changes in pH and temperature that alternate the chelating environment from 8- to 10-coordinate. This electron-withdrawing effect of the pyrazine backbone also deactivates the second amine after the first condensation addition of salicylaldehyde. Without a metal to template the complex formation reaction, even with extended reaction times and the addition of a large excess of ligand, the result is the addition of only one salicylaldehyde.

Heterometallic uranyl (hydroxyethyl)iminodiacetic acid (heidi) complexes: Molecular models for U(VI) uptake in complex media.

Amidoximated absorbents (AO-PAN) effectively remove U(VI) from aqueous solution, but previous studies reported more variability for complex natural waters that contain additional confounding ions and molecules. Ternary phases containing U(VI), M(III) (M = Fe(III), Al(III), Ga(III)), and organic molecules exist under these conditions and cause heterogeneous U(VI) uptake on AO-PAN. The goal of the current study is to provide additional insights into the structural features ternary complexes using N-(2-hydroxyethyl)-iminodiacetic acid (HEIDI) as the model organic chelator and explore the relevance of these species on U(VI) capture. Three model compounds ([(UO2)(Fe)2(µ3-O)(C6NO5H8)2(H2O)4] (UFe2), ([(UO2)(Al)2(µ2-OH)(C6NO5H8)2(H2O)3] (UAl2) and [(UO2)(Ga)2(µ2-OH)(C6NO5H8)2(H2O)3] (UGa2)) were characterized by single-crystal X-ray diffraction. Raman spectra of the model compounds were compared with solution data and the ternary phases were noted in the case of Al(III) and Ga(III), but not in the Fe(III) system. U(VI) adsorption onto AO-PAN was not impacted by the presence of HEIDI or the trivalent metal species.

1,8-Dihydroxy Naphthalene-A New Building Block for the Self-Assembly with Boronic Acids and 4,4'-Bipyridine to Stable Host-Guest Complexes with Aromatic Hydrocarbons.

The new Lewis acid-base adducts of general formula X(nad)B←NC5H4-C5H4N→B(nad)X [nad = 1,8-O2C10H6, X = C6H5 (2c), 3,4,5-F3-C6H2 (2d)] were synthesized in high yields via reactions of 1,8-dihydroxy naphthalene [nadH2] and 4,4'-bipyridine with the aryl boronic acids C6H5B(OH)2 and 3,4,5-F3-C6H2B(OH)2, respectively, and structurally characterized by multi-nuclear NMR spectroscopy and SCXRD. Self-assembled H-shaped Lewis acid-base adduct 2d proved to be effective in forming thermally stable host-guest complexes, 2d × solvent, with aromatic hydrocarbon solvents such as benzene, toluene, mesitylene, aniline, and m-, p-, and o-xylene. Crystallographic analysis of these solvent adducts revealed host-guest interactions to primarily occur via π···π contacts between the 4,4'-bipyridyl linker and the aromatic solvents, resulting in the formation of 1:1 and 1:2 host-guest complexes. Thermogravimetric analysis of the isolated complexes 2d × solvent revealed their high thermal stability with peak temperatures associated with the loss of solvent ranging from 122 to 147 °C. 2d, when self-assembled in an equimolar mixture of m-, p-, and o-xylene (1:1:1), preferentially binds to o-xylene. Collectively, these results demonstrate the ability of 1,8-dihydroxy naphthalene to serve as an effective building block in the selective self-assembly to supramolecular aggregates through dative covalent N→B bonds.

Colossal Anisotropic Thermal Expansion in a Diazo-Functionalized Compound with Switchable Solid-State Behavior.

Achieving substantial anisotropic thermal expansion (TE) in solid-state materials is challenging as most materials undergo volumetric expansion upon heating. Here, we describe colossal, anisotropic TE in crystals of an organic compound functionalized with two azo groups. Interestingly, the material exhibits distinct and switchable TE behaviors within different temperature regions. At high temperature, two-dimensional, area zero TE and colossal, positive linear TE (α=211 MK-1 ) are attained due to dynamic motion, while at low temperature, moderate positive TE occurs in all directions. Investigation of the solid-state motion showed the change in enthalpy and entropy are quite different in the two temperature regions and solid-state NMR experiments support motion in the solid. Cycling experiments demonstrate that the solid-state motions and TE behaviors are completely reversible. These results reveal strategies for designing significant anisotropic and switchable behaviors in solid-state materials.

Controlling Thermal Expansion in Supramolecular Halogen-Bonded Mixed Cocrystals through Synthetic Feed and Dynamic Motion.

Control over thermal expansion (TE) behaviors in solid materials is often accomplished by modifying the molecules or intermolecular interactions within the solid. Here, we use a mixed cocrystal approach and incorporate molecules with similar chemical structures, but distinct functionalities. Development of mixed cocrystals is at a nascent stage, and here we describe the first mixed cocrystals sustained by one-dimensional halogen bonds. Within each mixed cocrystal, the halogen-bond donor is fixed, while the halogen-bond acceptor site contains two molecules in a variable ratio. X-ray diffraction demonstrates isostructurality across the series, and SEM-EDS shows equal distribution of heavy atoms and similar atomic compositions across all mixed cocrystals. The acceptor molecules differ in their ability to undergo dynamic motion in the solid state. The synthetic equivalents of motion capable and incapable molecules were systematically varied to yield direct tunabililty in TE behavior.

Small Molecule Activation with Intramolecular "Inverse" Frustrated Lewis Pairs.

The intramolecular "inverse" frustrated Lewis pairs (FLPs) of general formula 1-BR2 -2-[(Me2 N)2 C=N]-C6 H4 (3-6) [BR2 =BMes2 (3), BC12 H8 , (4), BBN (5), BBNO (6)] were synthesized and structurally characterized by multinuclear NMR spectroscopy and X-ray analysis. These novel types of pre-organized FLPs, featuring strongly basic guanidino units rigidly linked to weakly Lewis acidic boryl moieties via an ortho-phenylene linker, are capable of activating H-H, C-H, N-H, O-H, Si-H, B-H and C=O bonds. 4 and 5 deprotonated terminal alkynes and acetylene to form the zwitterionic borates 1-(RC≡C-BR2 )-2-[(Me2 N)2 C=NH]-C6 H4 (R=Ph, H) and reacted with ammonia, BnNH2 and pyrrolidine, to generate the FLP adducts 1-(R2 HN→BR2 )-2-[(Me2 N)2 C=NH]-C6 H4 , where the N-H functionality is activated by intramolecular H-bond interactions. In addition, 5 was found to rapidly add across the double bond of H2 CO, PhCHO and PhNCO to form cyclic zwitterionic guanidinium borates in excellent yields. Likewise, 5 is capable of cleaving H2 , HBPin and PhSiH3 to form various amino boranes. Collectively, the results demonstrate that these new types of intramolecular FLPs featuring weakly Lewis acidic boryl and strongly basic guanidino moieties are as potent as conventional intramolecular FLPs with strongly Lewis acidic units in activating small molecules.

Thermal Expansion Properties and Mechanochemical Synthesis of Stoichiometric Cocrystals Containing Tetrabromobenzene as a Hydrogen- and Halogen-Bond Donor.

The solution and mechanochemical synthesis of two cocrystals that differ in the stoichiometric ratio of the components (stoichiometric cocrystals) is reported. The components in the stoichiometric cocrystals interact through hydrogen or hydrogen/halogen bonds and differ in π-stacking arrangements. The difference in structure and noncovalent interactions affords dramatically different thermal expansion behaviors in the two cocrystals. At certain molar ratios, the cocrystals are obtained concomitantly; however, by varying the ratios, a single stoichiometric cocrystal is achieved using mechanochemistry.

Self-Assembly of Complementary Components Using a Tripodal Bismuth Compound: Pnictogen Bonding or Coordination Chemistry?

Triple pnictogen bonding refers to the ability of a pnictogen atom to engage in three simultaneous pnictogen bonds (PnBs) to a complementary partner through a single pnictogen atom. This supramolecular strategy was recently introduced as a unique facet of pnictogen bonding as compared to other named supramolecular interactions. Here, the ability of bismuth to participate in this phenomenon is demonstrated using Bi((NC9H7)3CH3). The study reveals that Bi engages in stronger PnBs than the analogous Sb system. The results have been contrasted with Bi systems that form strong coordination bonds, and analysis of the electron density along the bond path reveals key differences. The solution behavior of these newly synthesized supramolecules were studied by PFGSE NMR spectroscopy and they are found to remain intact in solution. Molecular design strategies that allow for triple pnictogen bonding should find use in the fields of molecular recognition and crystal engineering.

Controlling Topology within Halogen-Bonded Networks by Varying the Regiochemistry of the Cyclobutane-Based Nodes.

The formation of a pair of extended networks sustained by halogen bonds based upon two regioisomers of a photoproduct, namely rctt-1,3-bis(4-pyridyl)-2,4-bis(phenyl)cyclobutane (ht-PP) and rctt-1,2-bis(4-pyridyl)-3,4-bis(phenyl)cyclobutane (hh-PP), that have varied topology is reported. These networks are held together via I⋯N halogen bonds between the photoproduct and the halogen-bond donor 1,4-diiodoperchlorobenzene (C6I2Cl4). The observed topology in each solid is controlled by the regiochemical position of the halogen-bond accepting 4-pyridyl group. This paper demonstrates the ability to vary the topology of molecular networks by altering the position of the halogen bond acceptor within the cyclobutane-based node.

Cobalt(II)-Catalyzed Stereoselective Olefin Isomerization: Facile Access to Acyclic Trisubstituted Alkenes.

Stereoselective synthesis of trisubstituted alkenes is a long-standing challenge in organic chemistry, due to the small energy differences between E and Z isomers of trisubstituted alkenes (compared with 1,2-disubstituted alkenes). Transition metal-catalyzed isomerization of 1,1-disubstituted alkenes can serve as an alternative approach to trisubstituted alkenes, but it remains underdeveloped owing to issues relating to reaction efficiency and stereoselectivity. Here we show that a novel cobalt catalyst can overcome these challenges to provide an efficient and stereoselective access to a broad range of trisubstituted alkenes. This protocol is compatible with both mono- and dienes and exhibits a good functional group tolerance and scalability. Moreover, it has proven to be a useful tool to construct organic luminophores and a deuterated trisubstituted alkene. A preliminary study of the mechanism suggests that a cobalt-hydride pathway is involved in the reaction. The high stereoselectivity of the reaction is attributed to both a π-π stacking effect and the steric hindrance between substrate and catalyst.

Triple-Pnictogen Bonding as a Tool for Supramolecular Assembly.

Supramolecular assembly utilizing simultaneous formation of three pnictogen bonds around a single antimony vertex was explored via X-ray crystallography, solution NMR, and computational chemistry. An arylethynyl (AE) ligand was designed to complement the three electrophilic regions around the Sb compound. Though solution studies reveal large binding constants for individual pyridyl units with the Sb donor, the rigidity and prearrangement of the AE acceptor proved necessary to achieve simultaneous binding of three acceptors to the Sb-centered pnictogen-bond donor. Calculations and X-ray structures suggest that negative cooperativity upon sequential binding of three acceptors to a Sb center limits the utility of triple-pnictogen bonding pyridyl acceptors. These limitations can be negated, however, when positive cooperativity is designed into a complementary acceptor ligand.

"Inverse" Frustrated Lewis Pairs: An Inverse FLP Approach to the Catalytic Metal Free Hydrogenation of Ketones.

For the first time have boron-containing weak Lewis acids been demonstrated to be active components of Frustrated Lewis Pair (FLP) catalysts in the hydrogenation of ketones to alcohols. Combining the organosuperbase (pyrr)3 P=NtBu with the Lewis acid 9-(4-CF3 -C6 H4 )-BBN generated an "inverse" FLP catalyst capable of hydrogenating a range of aliphatic and aromatic ketones including N-, O- and S-functionalized substrates and bio-mass derived ethyl levulinate. Initial computational and experimental studies indicate the mechanism of catalytic hydrogenation with "inverse" FLPs to be different from conventional FLP catalysts that contain strong Lewis acids such as B(C6 F5 )3 .

A pseudopericyclic [3,5]-sigmatropic rearrangement of a coumarin trichloroacetimidate derivative.

Thermolysis of a coumarin trichloroacetimidate yields a single rearrangement product. The proposed mechanism is a pseudopericyclic allowed (Woodward-Hoffman forbidden) [3,5]-sigmatropic rearrangement to form the corresponding amide followed by a sigmatropic [1,5]-hydrogen migration. Transition state calculations at the B3LYP/6-31G(d,p) level support this mechanism and suggest the selectivity is influenced by the stability of the intermediates.

Improved Synthesis of N-Methylcadaverine.

Alkaloids compose a large class of natural products, and mono-methylated polyamines are a common intermediate in their biosynthesis. In order to evaluate the role of selectively methylated natural products, synthetic strategies are needed to prepare them. Here, N-methylcadaverine is prepared in 37.3% yield in three steps. The alternative literature two-step strategy resulted in reductive deamination to give N-methylpiperidine as determined by the single crystal structure. A straightforward strategy to obtain the mono-alkylated aliphatic diamine, cadaverine, which avoids potential side-reactions, is demonstrated.

Asymmetric [3 + 2] Cycloaddition of Chiral N-Phosphonyl Imines with Methyl Isocyanoacetate for Accessing 2-Imidazolines with Switchable Stereoselectivity.

Asymmetric [3 + 2] cycloaddition of chiral N-phosphonyl imines with methyl isocyanoacetate has been established, enabling controllable/switchable stereoselectivity access to 21 examples of cycloadducts with good to excellent chemical yields (up to 92%) and high diastereoselectivities (up to 99:1 dr). The cycloaddition reaction promoted by Cs2CO3 resulted in diastereoenriched (4R,5S)-products with >99:1 dr. However, it showed the reverse stereoselectivity as diastereoenriched (4S,5R) products when AgF was employed as the catalyst. The synthesis followed the group-assisted purification (GAP) chemistry/technology in which the pure 2-imidazoline products were readily provided by washing the crude products with cosolvents of hexane and ethyl acetate.

Interactions of Verkade's Superbase with Strong Lewis Acids: From Labile Mono- and Binuclear Lewis Acid-Base Complexes to Phosphenium Cations.

A series of mono- and binuclear Lewis acid-base complexes of the formulas N[CH2CH2N(Pri)]3P→LA [LA = BH3 (8), Ga(C6F5)3 (10), GaCl3 (11)], LA←N[CH2CH2N(Pri)]3P [LA = Al(C6F5)3 (6a), AlMe3 (6b), AlEt3 (6c), AlBui3 (6d), BF3 (13)], and LA←N[CH2CH2N(Pri)]3P→LA [Lewis acid (LA) = Al(C6F5)3 (7a), AlMe3 (7b), AlEt3 (7c), AlBui3 (7d), AlCl3 (7e), BH3 (9)] were generated from reactions of Verkade's base, N[CH2CH2N(Pri)]3P (1), with various boron-, aluminum-, and gallium-containing Lewis acids, and characterized by multinuclear NMR spectroscopy. {N[CH2CH2N(Pri)]3P→C7H7}[BF4] (5) was synthesized via the treatment of 1 with [C7H7][BF4]. The reaction of 1 with B(C6F5)3, followed by the addition of [Ph3C]2[B12Cl12], gave rise to the rearranged borate salt [PN4C9H17(Pri)2][B12Cl12] (3), while treating 1 with [Ph3C]2[B12Cl12] exclusively afforded {N[CH2CH2N(Pri)]3PH}2[B12Cl12] (4). Reactions of 1 with 2 equiv of GaCl3 and BF3, respectively, afforded the novel phosphenium gallate and borate salts 12a, 12b, and 15. The solid-state structures of 1, 3-5, 6b, 7a, 7b, 7e, 8, 10, 11, 12b, 13, and 15 were determined by X-ray crystallography.

Zwitterionic Alkali-Metal Silanides of Tripodal Ligand Geometry: Synthesis, Structure, and Lewis Acid-Base Chemistry.

A unique family of zwitterionic alkali-metal silanides of general formula [Si(SiMe2OR)3M] (M-3), where M = Li, Na, K and R = CH2CH3 (M-3b), CH(CH3)2 (M-3c), CH2CH(CH3)2 (M-3d), CH2CH2OSCH3 (M-3g), CH2CH2N(CH3)2 (M-3h), have been synthesized and their structures fully characterized. Compounds M-3 were prepared from reactions of the corresponding alkali-metal alkoxides, R'OM (R' = But, Bui; M = Li, Na, K) with the silanes Si(SiMe2OR)4 (2a-h), where R = CH2CH3 (b), CH(CH3)2 (c), CH2CH(CH3)2 (d), CH2CH2OSCH3 (g), CH2CH2N(CH3)2 (h), via selective Si-Si bond cleavage. Analysis of the X-ray data of Li-3a-e,g, Li-h, Li-4, Na-3a-c,e,f,h, and K-3b,d,e,g revealed two major structural motifs in the solid state: infinite chain type and monomeric zwitterions. The reaction of Si(SiMe2OCH2CH3)3Li (Li-3b) with BPh3 in THF gave the zwitterionic Lewis acid-base complex Ph3BSi(SiMe2OCH2CH3)3Li·THF (Li-5b). Reactions of W(CO)6 with Li-3b-d and Na-3b,c resulted in the formation of the zwitterionic silyl tungstenate complexes (CO)5WSi[SiMe2OCH2CH3]3Li (Li-6b), (CO)5WSi[SiMe2OCH(CH3)2]3Li (Li-6c), (CO)5WSi[SiMe2OCH2CH(CH3)2)]3Li (Li-6d), (CO)5WSi(SiMe2OCH2CH3)3Na (Na-6b), and (CO)5WSi[SiMe2OCH(CH3)2]3Na (Na-6c), respectively. The solid-state structures of Li-5b and Na-6b were determined by X-ray crystallography.

Precise Steric Control over 2D versus 3D Self-Assembly of Antimony(III) Alkoxide Cages through Strong Secondary Bonding Interactions.

Antimony(III) alkoxide cages were designed as building blocks for predictable supramolecular self-assembly. Supramolecular synthons featuring two Sb···O secondary bonding interactions (SBIs), each SBI stronger than 30 kJ/mol, were used to drive the formation of the supramolecular architectures. Judicious choice of pendant groups provided predictable control over the formation of self-assembled 3D columnar helices, which crystallized with hollow morphologies, or a self-assembled 2D bilayer. The Sb-O stretching frequency provides a spectroscopic signature of Sb···O SBI formation.