Intramolecular O―H⋯O and C―H⋯O hydrogen bond cooperativity in D‐glucopyranose and D‐galactopyranose—A DFT/GIAO,QTAIM/IQA,and NCI approach

Density functional theory calculations are used to compute proton nuclear magnetic resonance (NMR) chemical shifts, interatomic distances, atom–atom interaction energies, and atomic charges for partial structures and conformers of α‐D‐glucopyranose, β‐D‐glucopyranose, and α‐D‐galactopyranose built up by introducing OH groups into 2‐methyltetrahydropyran stepwisely. For the counterclockwise conformers, the most marked effects on the NMR shift and the charge on the OH1 proton are produced by OH2, those of OH3 and OH4 being somewhat smaller. This argues for a diminishing cooperative effect. The effect of OH6 depends on the configuration of the hydroxymethyl group and the position, axial or equatorial, of OH4, which controls hydrogen bonding in the 1,3‐diol motif. Variations in the interaction energies reveal that a “new” hydrogen bond is sometimes formed at the expense of a preexisting one, probably due to geometrical constraints. Whereas previous work showed that complexing a conformer with pyridine affects only the nearest neighbour, successive OH groups increase the interaction energy of the N⋯H1 hydrogen bond and reduce its length. Analogous results are obtained for the clockwise conformers. The interaction energies for C―H⋯OH hydrogen bonding between axial CH protons and OH groups in certain conformers are much smaller than for O―H⋯OH bonds but they are largely covalent, whereas those of the latter are predominantly coulombic. These interactions are modified by complexation with pyridine in the same way as O―H⋯OH interactions: the computed NMR shifts of the CH protons increase, the atom–atom distances are shorter, and interaction energies are enhanced.     

Synthesis, structure and reactivity of cuboidal-type cluster aqua complexes with W3PdS4 4+ core

The reaction of PdCl(2) with [W3S4(H2O)9]4+ in the presence of hypophosphorous acid in 2 M HCl gives cuboidal cluster [W3(PdCl)S4(H2O)9]3+ (1) which undergoes condensation and crystallises from Hpts solutions as edge-linked double cubane cluster [{W3PdS4(H2O)9}2](pts)(8).19H2O (pts = p-toluenesulfonate) (1'). The substitution of Cl- in (1) by different ligands was explored. The Pd atom in the cluster shows an exceptionally high reactivity in the isomerisation of the hydrophosphoryl H2P(O)(OH), HP(O)(OH)2, HPPh(O)(OH) and HPPh2(O) molecules into the corresponding hydroxo tautomers HP(OH)2, P(OH)3, PhP(OH)2 and Ph2P(OH) stabilised by coordination at Pd. The reactions were followed by UV-Vis spectrophotometry and 31P NMR. Formation constants of the 1 : 1 coordination of [M3(PdCl)S4(H2O)9]3+ (M = Mo, W) with HP(OH)2 and As(OH)3 were obtained. The structures of cucurbit[6]uril (C36H36N24O12, CUC[6]) adducts [W3(PdP(OH)3)S4(H2O)8Cl]-(C36H36N24O12)Cl3.12.5H2O (2), and [W3Pd(PhP(OH)2)S4(H2O)7Cl2]2(C36H36N24O12)Cl4.9H2O (3) were determined by single-crystal X-ray diffraction.     

Influence of bond fixation in benzo-annulated N-salicylideneanilines and their ortho-C(=O)X derivatives (X = CH3, NH2, OCH3) on tautomeric equilibria in solution

1H, 13C, and 15N NMR spectra show that an ortho-C(=O)X group present in the molecules of N-salicylideneanthranilamide (X = NH2), methyl N-salicylideneanthranilate (X = OCH3), N-salicylidene-o-aminoacetophenone (X = CH3), and their benzo analogues have only a minor effect on the tautomeric OH/NH-equilibrium in solution. Only two of three possible tautomers were detected. Lability of the absent form was proved by theoretical calculations. Calculated energies show that the enolimino form (OH) is less stable than the enaminone (NH) form only for dibenzo-annulated N-salicylideneanilines. The population of each species in the tautomeric mixture was found to be inversely proportional to its energy. Application of the geometry-based aromaticity index HOMA shows that the effectiveness of the pi-electron delocalization in different rings in the molecule depends mostly on the position of benzo-annulation. Both the NH...O and N...HO hydrogen bonds present in the NH and OH tautomers, respectively, increase the aromaticity of the quasirings H-O-C=C-C=N and O=C-C=C-N-H and decrease the aromatic character of the fused benzene ring. These results seem to be reliable when N-salicylideneanilines studied are compared with naphthalene and their benzo-annulated derivatives, i.e., phenanthrene, anthracene, and triphenylene. An analysis of the effectiveness of pi-electron delocalization confirms that in all cases studied, the OH form is more stable. Although the HOMA values and calculated energies are not a criterion that allows determination of the dominating tautomer, both of these parameters correctly show the effect of changes in the molecular topology on tautomeric preferences.     

Intramolecular hydrogen-bonding interactions in 2-nitrosophenol and nitrosonaphthols: ab initio, density functional, and nuclear magnetic resonance theoretical study

Intramolecular hydrogen bonding (IHB) interactions and molecular structures of 2-nitrosophenol, nitrosonaphthols, and their quinone-monooxime tautomers were investigated at ab initio and density functional theory (DFT) levels. The geometry optimization of the structures studied was performed without any geometrical restrictions. Possible conformations with different types of the IHB of the tautomers were considered to understand the nature of the HB among these conformers. The effect of solvent on hydrogen bond energies, conformational equilibria, and tautomerism in aqueous solution were studied. Natural bond orbital analysis was performed to study the IHB in the gaseous phase and in aqueous medium. The NMR 1H, 13C, 15N, and 17O chemical shifts in the gaseous phase and in solution for the studied compounds were calculated using the gauge-including atomic orbitals approach implemented in the Gaussian 03 program package. The optimized geometrical parameters and 1H NMR chemical shifts are in good agreement with previous theoretical and experimental data.     

Density functional theory study of intramolecular hydrogen bonding and proton transfer in o-hydroxyaryl ketimines

The potential energy surface and the reaction pathway for the intramolecular hydrogen transfer in o-hydroxyaryl ketimines are characterized using DFT methods. Structural changes in the proton-transfer process in quasi-aromatic hydrogen bonding are described. A transition state and a state with a low proton-transfer barrier were studied in sterically compressed o-hydroxyaryl ketimines (2(N-methyl-alpha-iminoethyl)phenols) possessing two potential minimums. The potentials for proton vibration in the OH and HN tautomers of o-hydroxyaryl ketimines were investigated and anharmonic frequencies were determined. Solvent and substituent effects were analyzed. The energies of the various conformers of the OH and HN tautomers were compared with the related forms of o-hydroxyaryl aldimine.     

On the importance of intramolecular hydrogen bond cooperativity in d‐glucose – an NMR and QTAIM approach

The idea that hydrogen bond cooperativity is responsible for the structure and reactivity of carbohydrates is examined. Density functional theory and gauge‐including atomic orbital calculations on the known conformers of the α and β anomers of d ‐glucopyranose in the gas phase are used to compute proton NMR chemical shifts and interatomic distances, which are taken as criteria for probing intramolecular interactions. Atom–atom interaction energies are calculated by the interacting quantum atoms approach in the framework of the quantum theory of atoms in molecules. Association of OH1 in the counterclockwise conformers with a strong acceptor, pyridine, is accompanied by cooperative participation from OH2, but there is no significant change in the bonding of the two following 1,2‐diol motifs. The OH6 ^... O5 (G?g+/cc/t and G+g?/cc/t conformers) or OH6 ^... O4 (Tg+/cc/t conformer) distance is reduced, and the OH6 proton is slightly deshielded. In the latter case, this shortening and the associated increase in the OH6–O4 interaction energy may be interpreted as a small cooperative effect, but intermolecular interaction energies are practically the same for all three conformers. In most of the pyridine complexes, one ortho proton interacts with the endocyclic oxygen O5. Analogous results are obtained when the clockwise conformer, G?g+/cl/g?, detected for the α anomer, and a hypothetical conformer, Tt/cl/g?, are complexed with pyridine through OH6. Generally, the cooperative effect does not go beyond the first two OH groups of a chain. Copyright © 2017 John Wiley & Sons, Ltd.     

A solid state and solution NMR study of the tautomerism in hydroxyquinoline carboxylic acids

Some hydroxyquinoline carboxylic acids and their conjugate acids and bases were characterized by 13C and 15N NMR spectroscopy in solution and in the solid state. Differences in 13C and, in particular, 15N chemical shift patterns allow to distinguish between individual tautomers and confirm the presence of zwitterionic species in the solid state. Solution NMR spectra in dimethyl sulfoxide (DMSO) show effects resulting as a consequence of dynamic exchange and suggest the presence of an equilibrium mixture of hydroxyquinoline carboxylic acid and zwitterionic hydroxyquinolinium carboxylate tautomers.     

Crystal,molecular structure and tautomerism of (5-methyl-1H-[1,2,4]triazol-3-ylsulfanyl)-acetic acid

Molecular structure, relative stability of conformers, and tautomers of (5-methyl-1H-[1,2,4]triazol-3-ylsulfanyl)-acetic acid (MTSA) have been investigated by experimental (X-ray diffraction) and theoretical (B3LYP/aug-cc-pVDZ) methods. It was demonstrated that in the solid state MTSA exists in N1H tautomeric form. This tautomer is not the most stable in gas phase and its stabilization is provided by environment effects.     

The Role of Intramolecular Hydrogen Bonds vs. Other Weak Interactions on the Conformation of Hyponitrous Acid and Its Mono- and Dithio-Derivatives

High level ab initio and density functional theory calculations have been carried out to investigate the relative stability of the different conformers of hyponitrous acid and its mono- and dithio-derivatives. Geometries and vibrational frequencies were obtained at the B3LYP/6-311+G(d,p) level and final energies through B3LYP/6-311++G(3df,2pd) single point calculations. The reliability of this theoretical scheme has been assessed by comparing these DFT results with those obtained at the G3 level of theory, for some suitable cases. The cis conformers of hyponitrous acid and its mono- and dithio-derivatives are systematically more stable than the trans ones because in the cis conformation a dative interaction between the nitrogen-lone pairs and the σ_NX^* antibonding orbital is significantly favored. Quite interestingly, in general, the conformers presenting an intramolecular hydrogen bond (IHB) are not the global minima of the corresponding potential energy surfaces and only for hyponitrous acid the conformer with a OH ⋅s O IHB is slightly more stable than the cis conformer without IHB. The low stability of the tautomers with IHB is closely related with another weak intramolecular interaction which involves the lone-pairs of the chalcogen atoms and the π_NN^* antibondig orbital, and which is significantly perturbed when the IHB is formed.     

Tautomer selective photochemistry in 1-(tetrazol-5-yl)ethanol

A combined matrix isolation FTIR and theoretical DFT/B3LYP/6-311++G(d,p) study of the molecular structure and photochemistry of 1-(tetrazol-5-yl)ethanol [1-TE] was performed. The potential energy surface landscapes of the 1H and 2H tautomers of the compound were investigated and the theoretical results were used to help characterize the conformational mixture existing in equilibrium in the gas phase prior to deposition of the matrices, as well as the conformers trapped in the latter. In the gas phase, at room temperature, the compound exists as a mixture of 12 conformers (five of the 1H tautomer and seven of the 2H tautomer). Upon deposition of the compound in an argon matrix at 10 K, only three main forms survive, because the low barriers for conformational isomerization allow extensive conformational cooling during deposition. Deposition of the matrix at 30 K led to further simplification of the conformational mixture with only one conformer of each tautomer of 1-TE surviving. These conformers correspond to the most stable forms of each tautomer, which bear different types of intramolecular H-bonds: 1H-I has an NH···O hydrogen bond, whereas 2H-I has an OH···N hydrogen bond. Upon irradiating with UV light (λ > 200 nm), a matrix containing both 1H-I and 2H-I forms, an unprecedented tautomer selective photochemistry was observed, with the 2H tautomeric form undergoing unimolecular decomposition to azide + hydroxypropanenitrile and the 1H-tautomer being photostable.     

Structures, photoluminescence, and reversible vapoluminescence properties of neutral platinum(II) complexes containing extended pi-conjugated cyclometalated ligands

Reacting K2PtCl4 with the tridentate R-C(wedge)N(wedge)C-H2 ligands 2,6-di-(2'-naphthyl)-4-R-pyridine (R = H, 1a; Ph, 1b; 4-BrC6H4, 1c; 3,5-F2C6H3, 1d) in glacial acetic acid, followed by heating in dimethyl sulfoxide (DMSO), gave complexes [(R-C(wedge)N(wedge)C)Pt(DMSO)] (2a-d). In the crystal structures of 2a-c, the molecules are paired in a head-to-tail orientation with Pt...Pt separations >6.3 A, and there are extensive close C-H...pi (d = 2.656-2.891 A), pi...pi (d = 3.322-3.399 A), and C-H...O=S (d = 2.265-2.643 A) contacts. [(Ph-C(wedge)N(wedge)C)Pt(PPh3)] (3) was prepared by reacting 2b with PPh3. Reactions of 2a-d with bis(diphenylphosphino)methane (dppm) gave [(R-C(wedge)N(wedge)C)2Pt2(mu-dppm)] (4a-d). Both head-to-head (syn) and head-to-tail (anti) conformations were found for 4a.6CHCl3.C5H12, whereas only one conformation was observed for 4b.2CHCl3 (syn), 4c.3CH2Cl2 (syn), and 4d.2CHCl3 (anti). In the crystal structures of 4a-d, there are close intramolecular Pt...Pt contacts of 3.272-3.441 A in the syn conformers, and long intramolecular Pt...Pt separations of 5.681-5.714 A in the anti conformers. There are weak C-H...X (d = 2.497-3.134 A) and X...X (X = Cl or Br; d = 2.973-3.655 A) interactions between molecules 4a-d and occluded CHCl3/CH2Cl2 molecules, and their solvent channels are of varying diameters (approximately 9-28 A). Complexes 2a-d, 3, and 4a-d are photoluminescent in the solid state, with emission maxima at 602-643 nm. Upon exposure to volatile organic compounds, 4a shows a fast and reversible vapoluminescent response, which is most intense with volatile halogenated solvents (except CCl4). Powder X-ray diffraction analysis of desolvated 4a revealed a more condensed molecular packing of syn and anti complexes than crystal 4a.6CHCl3.C5H12.     

A computational investigation of the nitrogen-boron interaction in o-(N,N-dialkylaminomethyl)arylboronate systems

o-(N,N-Dialkylaminomethyl)arylboronate systems are an important class of compounds in diol-sensor development. We report results from a computational investigation of fourteen o-(N,N-dialkylaminomethyl)arylboronates using second-order M?ller-Plesset (MP2) perturbation theory. Geometry optimizations were performed at the MP2/cc-pVDZ level and followed by single-point calculations at the MP2/aug-cc-pVDZ(cc-pVTZ) levels. These results are compared to those from density functional theory (DFT) at the PBE1PBE(PBE1PBE-D)/6-311++G(d,p)(aug-cc-pVDZ) levels, as well as to experiment. Results from continuum PCM and CPCM solvation models were employed to assess the effects of a bulk aqueous environment. Although the behavior of o-(N,N-dialkylaminomethyl) free acid and ester proved to be complicated, we were able to extract some important trends from our calculations: (1) for the free acids the intramolecular hydrogen-bonded B-O-H···N seven-membered ring conformers 12 and 16 are found to be slightly lower in energy than the dative-bonded N→B five-membered ring conformers 10 and 14 while conformers 13 and 17, with no direct boron-nitrogen interaction, are significantly higher in energy than 12 and 16; (2) for the esters where no intramolecular B-O-H···N bonded form is possible, the N→B conformers 18 and 21 are significantly lower in energy than the no-interaction forms 20 and 23; (3) H(2)O insertion reactions into the N→B structures 10, 14, 18, and 21 leading to the seven-membered intermolecular hydrogen-bonded B···OH(2)···N ring structures 11, 15, 19, and 22 are all energetically favorable.     

Synthesis and characterization of (R-C5H14N2)2[Ga4(C2O4)(H2PO4)2(PO4)4].2H2O, a layered gallium phosphatooxalate containing a chiral amine

The first metal phosphatooxalate containing a chiral amine, (R-C5H14N2)2[Ga4(C2O4)(H2PO4)2(PO4)4].2H2O, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction and 31P MAS NMR spectroscopy. It crystallizes in the monoclinic space group P2(1) (No. 4) with a = 8.0248(4) A, b = 25.955(1) A, c = 9.0127(5) A, beta = 100.151(1) degrees, and Z = 2. The structure consists of GaO6 octahedra and GaO4 tetrahedra connected by coordinating C2O4(2-) and phosphate anions to form anionic sheets in the ac plane with charge-compensating diprotonated R-2-methylpiperazinium cations and water molecules between the layers. There is a good correlation between the NMR spectrum and the structure.     

Isoguanine formation from adenine

Several possible mechanisms underlying isoguanine formation when OH radical attacks the C(2) position of adenine (A?C?2) are investigated theoretically for the first time. Two steps are involved in this process. In the first step, one of two low-lying A?C?2???OH reactant complexes is formed, leading to C(2)-H(2) bond cleavage. Between the two reactant complexes there is a small isomerization barrier, which lies well below separated adenine plus OH radical. The complex dissociates to free molecular hydrogen and an isoguanine tautomer (isoG?1 or isoG?2). The local and activation barriers for the two pathways are very similar. This evidence suggests that the two pathways are competitive. After dehydrogenation, there are two possible routes for the second step of the reaction. One is direct hydrogen transfer, via enol-keto tautomerization, which has high local barriers for both tautomers and is not favored. The other option is indirect hydrogen transfer involving microsolvation by one water molecule. The water lowers the reaction barrier by over 20?kcal mol(-1) , indicating that water-mediated hydrogen transfer is much more favorable. Both A+OH(?) →isoG+H(?) reactions are exothermic and spontaneous. Among four isoguanine tautomers, isoG?1 has the lowest energy. Our findings explain why only the N(1)H and O(2)H tautomers of isolated isoguanine and isoguanosine have been observed experimentally.     

Imino tautomers of gas-phase guanine from mid-infrared laser spectroscopy

We reinvestigated the assignment of the three major guanine conformers detected via resonance enhanced two-photon ionization (R2PI) in supersonic expansions and present IR/UV double resonance spectra in the spectral region between 1500 and 1800 cm(-1). Comparison with B3LYP/TZVPP and RI-MP2/cc-pVQZ calculations shows that both conformers B and C are 7H-keto tautomers with an imine group in the 2-position. They differ only in the local conformation of the imine group but are otherwise identical. Conformer A is an amino-enol form with the OH group in the trans position.     

Synthesis, experimental and theoretical characterization of tetra dentate N,N'-dipyridoxyl (1,3-propylenediamine) salen ligand and its Co(III) complex

The new tetra dentate dianionic H2PS (N,N'-dipyridoxyl (1,3-propylenediamine)) Schiff-base ligand and its octahedral Co(III) salen complex [Co(PS)(H2O)(CH3OH)]+CH3COO(-) were synthesized, where coordinating atoms of H2PS (N,N,O(-),O(-)) occupied equatorial positions with H2O and CH3OH as axial ligands. The nature of the H2PS and its complex were determined by elemental and spectrochemical (IR, UV-vis, 1H NMR and Mass) analysis. Also, the fully optimized geometries and vibrational frequencies of them together with the 1H NMR chemical shifts of H2PS have been calculated using density functional theory (B3LYP) method. Obtained structural parameters are in good agreement with the experimental data reported for similar compounds. The calculated and experimental results confirmed the suggested structures for the ligand and complex.     

The tautomeric forms of cyameluric acid derivatives

The tautomerism of cyameluric acid C6N7O3H3 (1 a), cyamelurates and other heptazine derivatives has recently been studied by several theoretical investigations. In this experimental study we prepared stannyl and silyl derivatives of cyameluric acid (1 a): C6N7O3[Sn(C4H9)3]3 (3 a), C6N7O3[Sn(C2H5)3]3 (3 b), and C6N7O3[Si(CH3)3]3 (4). In order to investigate the structure of 1 a the mono- and dipotassium cyamelurate hydrates K(C6N7O3H2)2 H2O (5) and K2(C6N7O3H)1 H2O (6) were synthesized by UV/Vis-controlled titration of a potassium cyamelurate solution with aqueous hydrochloric acid. Compounds 3-6 were characterized by FTIR and solid-state NMR spectroscopy as well as simultaneous thermal analysis (TGA, DTA). The single crystal X-ray structures of the salts 5 and 6 show that the hydrogen atoms in both anions are localized on the peripheral nitrogen atoms. This indicates-in combination with the solid-state NMR studies-that the most stable tautomer of solid 1 a is the triketo form with C3h symmetry. However, derivatives of both the hydroxyl and the amido tautomers may be formed depending on the substituent atoms: The spectroscopic data and single crystal structures of compounds C6N7O3[Si(CH3)3]3 (4) and the solvate C6N7O3[Sn(C2H5)3]3C2H4Cl2 (3 b') show that the former is derived from the symmetric trihydroxy form of 1 a, while 3 b' crystallizes as a chain-like polymer, which contains the tin atoms as multifunctional building blocks, that is, bridging pentacoordinated Et3SnO2 and Et3SnON units as well as non-bridging four-coordinated Et3SnN units. The cyameluric nucleus is part of the polymeric chains of C6N7O3[Sn(C2H5)3]3C2H4Cl2 (3 b'), by the action of both tautomeric forms of cyameluric acid, the amide and the ester form.     

Stabilization of the tautomers HP(OH)2 and P(OH)3 of hypophosphorous and phosphorous acids as ligands

Treatment of [CpRu(PPh(3))(2)Cl] 1 with the stoichiometric amount of H(3)PO(2) or H(3)PO(3) in the presence of chloride scavengers (AgCF(3)SO(3) or TlPF(6)) yields compounds of formula [CpRu(PPh(3))(2)(HP(OH)(2))]Y (Y = CF(3)SO(3) 2a or PF(6) 2b) and [CpRu(PPh(3))(2)(P(OH)(3))]Y (Y = CF(3)SO(3) 3aor PF(6) 3b) which contain, respectively, the HP(OH)(2) and P(OH)(3) tautomers of hypophosphorous and phosphorous acids bound to ruthenium through the phosphorus atom. The triflate derivatives 2a and 3a react further with hypophosphorous or phosphorous acids to yield, respectively, the complexes [CpRu(PPh(3))(HP(OH)(2))(2)]CF(3)SO(3) 4 and [CpRu(PPh(3))(P(OH)(3))(2)]CF(3)SO(3) 5 which are formed by substitution of one molecule of the acid for a coordinated triphenylphosphine molecule. The compounds 2 and 3 are quite stable in the solid state and in solutions of common organic solvents, but the hexafluorophosphate derivatives undergo easy transformations in CH(2)Cl(2): the hypophosphorous acid complex 2b yields the compound [CpRu(PPh(3))(2)(HP(OH)(2))]PF(2)O(2) 6, whose difluorophosphate anion originates from hydrolysis of PF(6)(-); the phosphorous acid complex 3b yields the compound [CpRu(PPh(3))(2)(PF(OH)(2))]PF(2)O(2) 7, which is produced by hydrolysis of hexafluorophosphate and substitution of a fluorine for an OH group of the coordinated acid molecule. All the compounds have been characterized by elemental analyses and NMR measurements. The crystal structures of 2a, 3a and 7 have been determined by X-ray diffraction methods.     

Structural Relevance of Intramolecular H-Bonding in Ortho-Hydroxyaryl Schiff Bases: The Case of 3-(5-bromo-2-hydroxybenzylideneamino) Phenol

A new Schiff base compound, 3-(5-bromo-2-hydroxybenzylideneamino)phenol (abbreviated as BHAP) was synthesized and characterized by ¹H- and ¹³C- nuclear magnetic resonance and infrared spectroscopies. DFT/B3LYP/6-311++G(d,p) calculations were undertaken in order to explore the conformational space of both the E- and Z- geometrical isomers of the enol-imine and keto-amine tautomers of the compound. Optimized geometries and relative energies were obtained, and it was shown that the most stable species is the E-enol-imine form, which may exist in four low-energy intramolecularly hydrogen-bonded forms (I, II, V, and VI) that are almost isoenergetic. These conformers were concluded to exist in the gas phase equilibrium with nearly equal populations. On the other hand, the infrared spectra of the compound isolated in a cryogenic argon matrix (10 K) are compatible with the presence in the matrix of only two of these conformers (conformers II and V), while conformers I and VI convert to these ones by quantum mechanical tunneling through the barrier associated with the rotation of the OH phenolic group around the C–O bond. The matrix isolation infrared spectrum was then assigned and interpreted with help of the DFT(B3LYP)/6-311++G(d,p) calculated infrared spectra for conformers II and V. In addition, natural bond orbital (NBO) analysis was performed on the most stable conformer of the experimentally relevant isomeric form (E-enol-imino conformer V) to shed light on details of its electronic structure. This investigation stresses the fundamental structural relevance of the O–H···N intramolecular H-bond in o-hydroxyaryl Schiff base compounds.     

Reactivity of Mo3PdS4+ 4 Cluster: Evidence for New Ligands PhP(OH)2 and Ph2P(OH) and Structural Characterization of [Mo3(Pd(PPh3))S4(H2O)5Cl4]⋅0.5CH3OH⋅3H2O

Cuboidal cluster aqua complex [Mo₃(PdCl)S₄(H₂O)₉]³⁺ in 4M HCl causes isomerization of (HO)₂P(O)(H), (HO)P(O)(H)₂, PhP(O)(OH)(H), and Ph₂P(O)(H) into hydroxo tautomers P(OH)₃, HP(OH)₂, PhP(OH)₂, and Ph₂P(OH) which are stabilized by P coordination to the Pd atom in the cluster. The reactions were followed by ³¹P NMR and UV/Vis spectroscopy. Hypophosphorous acid H₂P(O)(OH) in the presence of the cluster is rapidly oxidized into phosphorous acid; the reaction can be made catalytic. Coordination of PPh₃ also takes place, giving [Mo₃(Pd(PPh₃))S₄(H₂O)₅Cl₄]0.5CH₃OH3H₂O, whose crystal structure was determined.