Synthesis and Regioselective Functionalization of Tetrafluorobenzo-[α]-Fused BOPYPY Dyes.

The synthesis of a new bis-BF2 tetrafluorobenzo-[α]-fused BOPYPY dye from 4,5,6,7-tetrafluoroisoindole and 2-hydrazinopyrazine is reported. The regioselectivity of nucleophilic substitution reactions at the periphery of the tetrafluorinated BOPYPY and its α-bromo derivative were investigated using N-, O-, S-, and C-based nucleophiles. Among the aromatic fluorine atoms, the F2 atom is consistently regioselectively substituted, except when the α-position contains a thiophenol group; in this case, F4 is substituted instead due to stabilizing π-π-stacking between the two aromatic groups. The α-bromo BOPYPY derivative also reacts under Stille cross-coupling reaction conditions to produce the corresponding α-substituted product. The spectroscopic properties of these new fluorinated BOPYPYs were investigated and compared with nonfluorinated analogs.

Temperature-dependent solid-state phase transition with twinning in the crystal structure of 4-meth-oxy-anilinium chloride.

At room temperature, the title salt, C7H10NO+·Cl-, is ortho-rhom-bic, space group Pbca with Z' = 1, as previously reported [Zhao (2009 ▸). Acta Cryst. E65, o2378]. Between 250 and 200 K, there is a solid-state phase transition to a twinned monoclinic P21/c structure with Z' = 2. We report the high temperature structure at 250 K and the low-temperature structure at 100 K. In the low-temperature structure, the -NH3 hydrogen atoms are ordered and this group has a different orientation in each independent mol-ecule, in keeping with optimizing N-H⋯Cl hydrogen bonding, some of which are bifurcated: these hydrogen bonds have N⋯Cl distances in the range 3.1201 (8)-3.4047 (8) Å. In the single cation of the high-temperature structure, the NH hydrogen atoms are disordered into the average of the two low-temperature positions and the N⋯Cl hydrogen bond distances are in the range 3.1570 (15)-3.3323 (18) Å. At both temperatures, the meth-oxy group is nearly coplanar with the rest of the mol-ecule, with the C-C-O-C torsion angles being -7.0 (2)° at 250 K and -6.94 (12) and -9.35 (12)° at 100 K. In the extended ortho-rhom-bic structure, (001) hydrogen-bonded sheets occur; in the monoclinic structure, the sheets propagate in the (010) plane.

5,6-Di-methyl-benzo[d][1,3]oxatellurole.

The structure of the title compound, C9H10OTe, at 100 K has ortho-rhom-bic (P21212) symmetry with two independent mol-ecules in the asymmetric unit (Z' = 2). The mol-ecules are folded along their Te⋯O axes, with their Te-C-O planes angled at an average of 25.1° with respect to the remaining non-H atoms, which are almost coplanar (average deviation from planarity = 0.04 Å). A Hirshfeld plot shows weak inter-molecular inter-actions between the two Te atoms located in each asymmetric mol-ecule, with a Te⋯Te distance of 3.7191 (4) Å. The structure is strongly pseudosymmetric to the space group Pccn with Z' = 1. The crystal chosen for data collection was found to be was an inversion twin.

5- and 10-oxocorroles from ß-octaalkylcorroles.

The reaction of Zn ions with ß-octaalkylcorroles leads to the air oxidation of the macrocycle, with the formation of a mixture of 5- and 10-oxocorroles. Spectroscopic characterization confirms the antiaromatic character of these macrocycles. A simple synthetic protocol opens the way for more detailed studies of oxocorrole chemistry.

l-Me-thion-yl-l-tyrosine monohydrate.

The study of the oxidation of various proteins necessitates scrutiny of the amino acid sequence. Since me-thio-nine (Met) and tyrosine (Tyr) are easily oxidized, peptides that contain these amino acids are frequently studied using a variety of oxidation methods, including, but not limited to, pulse radiolysis, electrochemical oxidation, and laser flash photolysis. To date, the oxidation of the Met-Tyr dipeptide is not fully understood. Several investigators have proposed a mechanism of intra-molecular electron transfer between the sulfide radical of Met and the Tyr residue. Our elucidation of the structure and absolute configuration of l-Met-l-Tyr monohydrate, C14H20N2O4S·H2O (systematic name: (2S)-2-{[(2S)-2-amino-4-methyl-sulfanyl-butano-yl]amino}-3-(4-hy-droxy-phen-yl)propanoic acid monohydrate) is presented herein and provides information about the zwitterionic nature of the dipeptide. We suspect that the zwitterionic state of the dipeptide and its inter-action within the solvent medium may play a major role in the oxidation of the dipeptide. In the crystal, all the potential donor atoms inter-act via strong N-H⋯O, C-H⋯O, O-H⋯S, and O-H⋯O hydrogen bonds.

N-(4-Eth-oxy-phen-yl)-3-oxobutanamide.

The title compound, C12H15NO3, crystallizes with Z' = 2 in space group Pca21 with the two independent mol-ecules having almost the same conformation, differing mostly at the end of the butanamide chain. A local inversion center near 1/8, 3/4, z relates the two mol-ecules, as is common for structures in this space group with Z' = 2. The mol-ecule crystallizes as the keto tautomer, and the ß-diketone moieties are twisted out of planarity, with O-C⋯C-O pseudo torsion angles of -74.4 (5) and -83.9 (5)°. The N-H group of each independent mol-ecule donates an inter-molecular hydrogen bond to an amide carbonyl oxygen atom by positive or negative translations along the b axis, thus forming anti-parallel chains propagating in the [010] direction.

Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions.

We report an enantioselective synthesis of cyclic ketones with full substitutions at the α-positions in a highly diastereoselective manner. Our method is achieved by subjecting substrate motifs in 2-allyloxyenones to chiral organomagnesium reagents, which trigger the Claisen rearrangement upon direct 1,2-carbonyl addition. The observed diastereoselectivity of the allyl migration is proposed to originate from the intramolecular chelation of the magnesium alkoxide to the allyloxy moiety.

Palladium Complexes of N-Methylcorroles.

Alkylation of one of the inner-core nitrogen atoms is one possible approach to obtain dianionic corrole ligands, suitable for the coordination of divalent metal ions, such as PdII . Inner-core N-methylation can be obtained by treating the corrole with CH3 I, but the reaction conditions should be optimized to limit the formation of the dimethylated derivative. Two regioisomers, the N-21 and the N-22 methyl derivatives are obtained from the reaction, with the first product achieved in a higher amount. Structural characterization of the reaction products evidenced the distortion induced by the introduction of the methyl groups; the N-methylcorroles are chiral compounds, and the enantiomers were separated by chromatography, with their absolute configuration assigned by ECD computation. Palladium insertion was achieved in the case of monosubstituted corroles, but not with the dimethylated macrocycle; X-ray characterization of the complexes showed the distortion of the macrocycles. The Pd complexes do not show luminescence emission, but are able to produce singlet oxygen upon irradiation. The PdII complexes were also inserted in human serum albumin (HSA) and dispersed in water; in this case, the protein protects the corroles from photobleaching, and a switch from the type II to the type I mechanism in reactive oxygen species (ROS) production is observed.

Phosphine substitution and linkage isomerization in cyclopentadienylruthenium bis(triphenylphosphine)thiocyanide and selenocyanide, CpRu(PPh3)2NCS and CpRu(PPh3)2SeCN.

The reaction between CpRu(PPh3)2NCS (1a) and PMePh2 yields CpRu(PPh3)(PMePh2)NCS (2a) while CpRu(PPh3)(PMePh2)Cl reacts with SCN- to form the S-bonded isomer, CpRu(PPh3)(PMePh2)SCN (2b). Compound 1a and the linkage isomers of 2 were characterized by X-ray crystallography. The kinetics of the reaction between 1a and PMePh2 under pseudo-first order conditions in THF and in fluorobenzene to form 2a are consistent with a dissociative interchange mechanism. Activation parameters for the reaction are: ΔH† = 15.7 ± 0.6 kcal mol-1 and ΔS† = -35 ± 2 cal mol-1 K-1 in THF vs. ΔH† = 24.8 ± 1.2 kcal mol-1 and ΔS† = -6 ± 4 cal mol-1 K-1 in C6H5F. In the presence of added SCN-, the rate of phosphine substitution is unchanged but a mixture of 2a and 2b is observed. The selenocyanate derivative, CpRu(PPh3)2SeCN (3b), crystallizes as the Se-bonded linkage isomer. Compound 3b reacts with PMePh2 under pseudo-first order conditions in fluorobenzene to form CpRu(PPh3)(PMePh2)SeCN (4b) at a much faster rate than 1a with activation parameters: ΔH† = 30.9 ± 4.8 kcal mol-1 and ΔS† = 22.4 ± 15.9 cal mol-1 K-1 with no evidence for linkage isomerization to the N-bonded products.

Cationic Cobalt(II) Bisphosphine Hydroformylation Catalysis: In Situ Spectroscopic and Reaction Studies.

[HCo(CO)x(bisphosphine)](BF4), x = 1-3, is a highly active hydroformylation catalyst system, especially for internal branched alkenes. In situ infrared spectroscopy (IR), electron paramagnetic resonance (EPR), and nuclear magnetic resonance studies support the proposed catalyst formulation. IR studies reveal the formation of a dicationic Co(I) paramagnetic CO-bridged dimer, [Co2(µ-CO)2(CO)(bisphosphine)2]2+, at lower temperatures formed from the reaction of two catalyst complexes via the elimination of H2. DFT studies indicate a dimer structure with square-pyramidal and tetrahedral cobalt centers. This monomer-dimer equilibrium is analogous to that seen for HCo(CO)4, reacting to eliminate H2 and form Co2(CO)8. EPR studies on the catalyst show a high-spin (S = 3/2) Co(II) complex. Reaction studies are presented that support the cationic Co(II) bisphosphine catalyst as the catalyst species present in this system and minimize the possible role of neutral Co(I) species, HCo(CO)4 or HCo(CO)3(phosphine), as catalysts.

8(meso)-Pyridyl-BODIPYs: Effects of 2,6-Substitution with Electron-Withdrawing Nitro, Chloro, and Methoxycarbonyl Groups.

The introduction of electron-withdrawing groups on 8(meso)-pyridyl-BODIPYs tends to increase the fluorescence quantum yields of this type of compound due to the decrease in electronic charge density on the BODIPY core. A new series of 8(meso)-pyridyl-BODIPYs bearing a 2-, 3-, or 4-pyridyl group was synthesized and functionalized with nitro and chlorine groups at the 2,6-positions. The 2,6-methoxycarbonyl-8-pyridyl-BODIPYs analogs were also synthesized by condensation of 2,4-dimethyl-3-methoxycarbonyl-pyrrole with 2-, 3-, or 4-formylpyridine followed by oxidation and boron complexation. The structures and spectroscopic properties of the new series of 8(meso)-pyridyl-BODIPYs were investigated both experimentally and computationally. The BODIPYs bearing 2,6-methoxycarbonyl groups showed enhanced relative fluorescence quantum yields in polar organic solvents due to their electron-withdrawing effect. However, the introduction of a single nitro group significantly quenched the fluorescence of the BODIPYs and caused hypsochromic shifts in the absorption and emission bands. The introduction of a chloro substituent partially restored the fluorescence of the mono-nitro-BODIPYs and induced significant bathochromic shifts.

N-(4-Meth-oxy-3-nitro-phen-yl)acetamide.

The title compound, C9H10N2O4, crystallizes with a disordered nitro group in twinned crystals. Both the meth-oxy group and the acetamide groups are nearly coplanar with the phenyl ring, and the C-N-C-O torsion angle [0.2 (4)°] is also insignificantly different from zero. Overall, the 12-atom meth-oxy-phenyl-acetamide group is nearly planar, with an r.m.s. deviation of 0.042 Å. The nitro group is twisted out of this plane by about 30°, disordered into two orientations with opposite senses of twist. In the crystal, the N-H group donates a hydrogen bond to a nitro oxygen atom, generating chains propagating in the [101] direction. The amide carbonyl oxygen atom is not involved in the hydrogen bonding.

rac-N-(4-Eth-oxy-phen-yl)-3-hy-droxy-butanamide.

In the title compound, racemic bucetin [systematic name: N-(4-eth-oxy-phen-yl)-3-hydroxy-butanamide], C12H17NO3, the mol-ecule is in an extended conformation as illustrated by the C-O-C-C torsion angle [170.14 (15)°] in the eth-oxy group and the subsequent C-N-C-C [-177.24 (16)°], N-C-C-C [170.08 (15)°] and C-C-C-C [171.41 (15)°] torsion angles in the butanamide chain. In the crystal, the O-H group donates an inter-molecular O-H⋯O hydrogen bond to the amide carbonyl oxygen atom and also accepts an inter-molecular N-H⋯O hydrogen bond from an adjacent N-H group. The former forms 12-membered dimeric rings about inversion centers, and the latter form chains in the [001] direction. The overall hydrogen-bonded network is two-dimensional, with no propagation in the [100] direction.

Anion receptors with nitrone C-H hydrogen bond donors.

We report the use of nitrone C-H groups as hydrogen bond donors for binding anions. Acyclic anion receptors with two nitrone moieties were synthesized by condensation reactions between aryl-aldehydes and m-phenylenedihydroxylamines. The solid-state structure of dinitrones revealed C-H⋯O hydrogen bonds. Anion binding properties were investigated using NMR titration with halide and phosphate salts.

The Role of Anionic Ligands on Photoreactivity in Mo(VI) Dioxo Complexes of the Form MoO2 X2 (NN).

The photoreactivity of d0 metal dioxo complexes in activating C-H bonds has been recently studied.[1-3] We have previously reported that MoO2 Cl2 (bpy-t Bu) is an effective platform for light initiated C-H activation with unique product selectivity for the overall functionalization.[1] Herein we expand on these studies and report the synthesis and photoreactivity of several new Mo(VI) dioxo complexes with the general formula MoO2 (X)2 (NN); where X=F- , Cl- , Br- , CH3 - , PhO- , t BuO- and NN=2,2'-bipyridine (bpy) or 4,4'-tert-butyl-2,2'bipyridine (bpy-t Bu). Among these compounds, MoO2 Cl2 (bpy-t Bu) and MoO2 Br2 (bpy-t Bu) are able to participate in bimolecular photoreactivity with several substrates containing C-H bonds of various types such as allyls, benzyls, aldehydes (RCHO) and alkanes. MoO2 (CH3 )2 bpy and MoO2 (PhO)2 bpy do not participate in bimolecular photoreactions and instead they undergo photodecompositions. Computational studies indicate that the nature of the HOMO and LUMO is critical in supporting photoreactivity, with access to an LMCT (bpy→Mo) being necessary for tractable hydrocarbon functionalization.

1H-Benzo[g]pteridine-2,4-dione.

The structure of the title compound, C10H6N4O2, reported by Smalley et al. [(2021). Cryst. Growth Des. 22, 524-534] from powder diffraction data and 15N NMR spectroscopy, is confirmed using low-temperature data from a twinned crystal. The tautomer in the solid state is alloxazine (1H-benzo[g]pteridine-2,4-dione) rather than isoalloxazine (10H-benzo[g]pteridine-2,4-dione). In the extended structure, the mol-ecules form hydrogen-bonded chains propagating in the [01] direction through alternating centrosymmetric R 2 2(8) rings with pairwise N-H⋯O inter-actions and centrosymmetric R 2 2(8) rings with pairwise N-H⋯N inter-actions. The crystal chosen for data collection was found to be a non-merohedral twin (180° rotation about [001]) in a 0.446 (4):0.554 (6) domain ratio.

N-(4-Meth-oxy-2-nitro-phen-yl)acetamide.

In the title compound, C9H10N2O4, the three substituents vary in the degree of lack of planarity with the central phenyl ring. The meth-oxy group is nearest to being coplanar, with a C-C-O-C torsion angle of 6.1 (5)°. The nitro group is less coplanar, with a 12.8 (5)° twist about the C-N bond and the acetamido group is considerably less coplanar with the central ring, having a 25.4 (5)° twist about the C-N bond to the ring. The NH group forms an intra-molecular N-H⋯O hydrogen bond to a nitro-group O atom.

[1,4]Ditellurino[2,3-b:5,6-b']di-pyrazine.

[1,4]Ditellurino[2,3-b:5,6-b']di-pyrazine represents the first reported [1,4]chalcogena[2,3-b:5,6-b']di-pyrazine containing a heavy chalcogens The asymmetric unit consists of three mol-ecules. In contrast to its sulfur analog, which is planar [Lynch et al. (1994 ▸) Cryst. Struct. Commun. 50,1470-1472], C8H4N4Te2 is folded along the Te⋯Te axis to accommodate the larger chalcogenide atoms. The dihedral angle between the two Te2C2 rings of the central ring is 57.9° (mean of three). C-Te bond lengths range from 2.1105 (16) Što 2.1381 (17) Å, in good agreement with those predicted by their covalent radii. All Te atoms are involved in inter-molecular Te⋯N contacts, with distances in the range 2.894 (2) to 2.963 (2) Å. These result in a spiral supra-molecular assembly, forming helical columns.

N-(4-Hy-droxy-2-nitro-phen-yl)acetamide.

The title compound, C8H8N2O4, differs in its degree of planarity from the 3-nitro isomer and also in its hydrogen-bonding pattern. Its NH group forms an intra-molecular hydrogen bond to a nitro oxygen atom, and its OH group forms an inter-molecular hydrogen bond to an amide oxygen atom, generating [10] chains in the crystal.

Light-Initiated C-H Activation via Net Hydrogen Atom Transfer to a Molybdenum(VI) Dioxo.

MoO2Cl2(bpy-tBu) (1) is shown to be a potent one-electron oxidant upon irradiation with 365 nm light in various solvents, while being a weak two-electron oxidant in the dark. Complex 1 is characterized to activate various types of C-H bonds photochemically, including allylic and benzylic positions as well as alkanes and aldehydes. In all of these oxidations, 1 ultimately forms a bimetallic Mo(V)/Mo(V) species with a µ-oxo ligand (2). Depending on the substrate, the major organic product is identified as either an oxygenated or a C-C coupled (homodimerized) compound along with a minor chlorinated species. The product selectivity is proposed to be dependent upon the relative values between the bond dissociation enthalpy (BDE) of a potentially new C-OH bond within the product versus the BDE of a Mo-OH motif within a Mo(V)O(OH) intermediate. Based on this, we can estimate the BDE for Mo-OH to be 83-93 kcal/mol. Mechanistic studies suggest that the C-H activation occurs via a net hydrogen atom transfer (HAT) from 1* occurring either asynchronously or via a stepwise electron-proton transfer (ET-PT) process. Complex 2 is further demonstrated to reform dioxo 1 in the presence of chemical oxidants.