Probing the Local Magnetic Structure of the [FeIII (Tp)(CN)3 ]- Building Block Via Solid-State NMR Spectroscopy, Polarized Neutron Diffraction, and First-Principle Calculations.

The local magnetic structure in the [FeIII (Tp)(CN)3 ]- building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands: Spin-polarization on the carbon atoms and spin-delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab-initio calculations allowed us to connect the experimental spin-density map characterized by PND and the suggested distribution of the spin-density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point-dipole model. These discrepancies underline the limitation of the point-dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo-contact contributions.

Synthesis, crystal structures, and magnetic properties of a new family of heterometallic cyanide-bridged Fe(III)2M(II)2 (M=Mn, Ni, and Co) square complexes.

New heterobimetallic tetranuclear complexes of formula [Fe(III){B(pz)(4)}(CN)(2)(µ-CN)Mn(II)(bpy)(2)](2)(ClO(4))(2)·CH(3)CN (1), [Fe(III){HB(pz)(3)}(CN)(2)(µ-CN)Ni(II)(dmphen)(2)](2)(ClO(4))(2)·2CH(3)OH (2a), [Fe(III){B(pz)(4)}(CN)(2)(µ-CN)Ni(II)(dmphen)(2)](2)(ClO(4))(2)·2CH(3)OH (2b), [Fe(III){HB(pz)(3)}(CN)(2)(µ-CN)Co(II)(dmphen)(2)](2)(ClO(4))(2)·2CH(3)OH (3a), and [Fe(III){B(pz)(4)}(CN)(2)(µ-CN)Co(II)(dmphen)(2)](2)(ClO(4))(2)·2CH(3)OH (3b), [HB(pz)(3)(-) = hydrotris(1-pyrazolyl)borate, B(Pz)(4)(-) = tetrakis(1-pyrazolyl)borate, dmphen = 2,9-dimethyl-1,10-phenanthroline, bpy = 2,2'-bipyridine] have been synthesized and structurally and magnetically characterized. Complexes 1-3b have been prepared by following a rational route based on the self-assembly of the tricyanometalate precursor fac-[Fe(III)(L)(CN)(3)](-) (L = tridentate anionic ligand) and cationic preformed complexes [M(II)(L')(2)(H(2)O)(2)](2+) (L' = bidentate α-diimine type ligand), this last species having four blocked coordination sites and two labile ones located in cis positions. The structures of 1-3b consist of cationic tetranuclear Fe(III)(2)M(II)(2) square complexes [M = Mn (1), Ni (2a and 2b), Co (3a and 3b)] where corners are defined by the metal ions and the edges by the Fe-CN-M units. The charge is balanced by free perchlorate anions. The [Fe(L)(CN)(3)](-) complex in 1-3b acts as a ligand through two cyanide groups toward two divalent metal complexes. The magnetic properties of 1-3b have been investigated in the temperature range 2-300 K. A moderately strong antiferromagnetic interaction between the low-spin Fe(III) (S = 1/2) and high-spin Mn(II) (S = 5/2) ions has been found for 1 leading to an S = 4 ground state (J(1) = -6.2 and J(2) = -2.7 cm(-1)), whereas a moderately strong ferromagnetic interaction between the low-spin Fe(III) (S = 1/2) and high-spin Ni(II) (S = 1) and Co(II) (S = 3/2) ions has been found for complexes 2a-3b with S = 3 (2a and 2b) and S = 4 (3a and 3b) ground spin states [J(1) = +21.4 cm(-1) and J(2) = +19.4 cm(-1) (2a); J(1) = +17.0 cm(-1) and J(2) = +12.5 cm(-1) (2b); J(1) = +5.4 cm(-1) and J(2) = +11.1 cm(-1) (3a); J(1) = +8.1 cm(-1) and J(2) = +11.0 cm(-1) (3b)] [the exchange Hamiltonian being of the type H = -J(S(i)·S(j))]. Density functional theory (DFT) calculations have been used to substantiate the nature and magnitude of the exchange magnetic coupling observed in 1-3b and also to analyze the dependence of the exchange magnetic coupling on the structural parameters of the Fe-C-N-M skeleton.

Insecticidal cyclodepsipeptides from Beauveria felina.

A novel cyclodepsipeptide, iso-isariin B (1), and the known isaridin E (2) were isolated from the entomopathogenic fungus Beauveria felina. Their structures were elucidated using MS/MS fragmentation and extensive 2D-heteronuclear NMR. The X-ray structure of isaridin E was obtained, showing two potent intramolecular H bonds and a type-VI turn with the HyLeu(1)-Pro(2) amide bond in a cis conformation. Iso-isariin B (1) was active against the pest-insect Sitophilus spp. with an LD(50) value of 10 µg/mL. This observation also gives some clues for ecological interpretation of cyclodepsipeptide production by B. felina.

Dimensionality switching through a thermally induced reversible single-crystal-to-single-crystal phase transition in a cyanide complex.

The heterometallic hexanuclear cyanide-bridged complex {[Mn(bpym)(H(2)O)](2)[Fe(HB(pz)(3))(CN)(3)](4)} (1), its C(15)N and D(2)O enriched forms {[Mn(bpym)(H(2)O)](2)[Fe(HB(pz)(3))(C(15)N)(3)](4)} (2) and {[Mn(bpym)(D(2)O)](2)[Fe(HB(pz)(3))(CN)(3)](4)} (3), and the hexanuclear derivative complex {[Mn(bpym)(H(2)O)](2)[Fe(B(pz)(4))(CN)(3)](4)}·4H(2)O (4) [bpym = 2,2'-bipyrimidine, HB(pz)(3)(-) = hydrotris(1-pyrazolyl)borate, B(pz)(4)(-) = tetra(1-pyrazolyl)borate] have been synthesized. Their structures have been determined through single-crystal X-ray crystallography at different temperatures. Whereas 3 and 4 maintain a discrete hexanuclear motif during the entire temperature range investigated (down to 95 K), 1 and 2 exhibit a thermally induced reversible single-crystal to single-crystal phase transition driven by a remarkable concerted rearrangement of hydrogen and cyanide coordination bonds. While hexanuclear complexes are observed in the high temperature phases (noted 1a and 2a) above 200 K, the low temperature phases are composed of one-dimensional coordination polymers noted 1b and 2b. The magnetic properties of the four compounds have been investigated in the 2-300 K range, and they reveal the occurrence of an overall antiferromagnetic behavior. The thermal dependence of the optical reflectivity and the FT-IR absorbance have been studied for 1 in the range 10-300 K and 130-300 K, respectively. A comparative analysis of the structural and electronic properties for 1-4 clearly underlines the major role of the intermolecular interactions in the topological and dimensional rearrangement observed during the structural phase transition. This result opens new perspectives in the design of cyanide-based switchable magnetic materials using coordination bonds rearrangements.

Lactonizations of carboxylic acid-substituted 3-fluorodihydropyridines with electrophiles: peculiar behaviour of F(+).

Whereas for 3-fluorodihydropyridine-substituted carboxylic acids electrophiles such as HCl, iodine, bromine and peracids discriminate the double bond lacking and that bearing fluorine, no such differentiation took place in the case of electrophilic fluorine since the formation of both mono and gem-difluorolactones took place.

A quinhydrone-type 2 ratio 1 acceptor-donor charge transfer complex obtained via a solvent-free reaction.

A 2 : 1 2-methoxybenzoquinone (BQ(OMe))-hydroquinone (H2Q) complex (5), obtained as single crystals by a solvent-free reaction, combines dipolar and pi-pi interactions, as well as hydrogen bonding.

A new organometallic heteropolytungstate related to [Sb2W22O74(OH)2](12-): synthesis and structural characterisation of the bis-{Ru(p-cymene)}(2+)-containing anion [Sb2W20O70{Ru(p-cymene)}2](10-).

The easy synthesis of [Sb2W20O70{Ru(p-cymene)}2](10-) by the reaction between the organometallic precursor [Ru(p-cymene)Cl2]2 and [Sb2W20O70]14-, formed in situ, confirms the importance of the organometallic route to well defined ruthenium(+II)-substituted heteropolytungstates.

Coordination chemistry of the hexavacant tungstophosphate [H2P(2W12O48]12-: synthesis and characterization of iron(III) complexes derived from the unprecedented {P2W14O54} fragment.

Clusters which display the rare cubic Fe8 topology have been obtained by reaction of the metastable hexavacant polyoxotungstate [H2P2W12O48]12- with basic trinuclear metal acetates.

Organic-Inorganic Hybrids Based on Polyoxometalates. 5.(1) Synthesis and Structural Characterization of Bis(organophosphoryl)decatungstosilicates [gamma-SiW(10)O(36)((RPO)(2)](4)(-).

Organophosphoryl polyoxotungstate derivatives [gamma-SiW(10)O(36)(RPO)(2)](4)(-) (R = H (1), Et (2), n-Bu (3), t-Bu (4), C(2)H(4)COOH (5), Ph (6)) have been obtained by reaction of the divacant [gamma-SiW(10)O(36)](8)(-) anion with organophosphonic acids RPO(OH)(2) in acetonitrile. These new heteropolyanions have been characterized by elemental analysis, infrared spectroscopy, multinuclear ((1)H, (29)Si, (31)P, and (183)W) NMR, and X-ray crystallography. Crystals of (NBu(4))(2)(NEt(4))H[gamma-SiW(10)O(36)(C(6)H(5)PO)(2)] (anion 6) are monoclinic, space group P2(1), with lattice constants a = 16.489(4) Å, b = 14.016(3) Å, c = 18.542(8) Å, beta = 91.30(3) degrees, and Z = 2. The hybrid anion has a structure of virtual C(2v)() symmetry with two phenylphosphonate groups grafted to the surface of the divacant tungstosilicate. (183)W and (31)P NMR spectra of NBu(4) salts in DMF solution agree with the solid-state structure and the virtual C(2)(v)() symmetry.

Asymmetric synthesis of the oxygenated polycyclic system of (+)-harringtonolide.

A straightforward asymmetric synthesis of the cage oxygenated structure of (+)-harringtonolide has been accomplished for the first time. The key steps involved (i) a templated stereoselective IMDA reaction to build a highly functionalized cyclohexene ring D, (ii) functionalization of the cycloadduct, (iii) ring-closing metathesis providing the five-membered ring C, and finally (iv) a challenging one-step cascade cyclization of an epoxy-alcohol toward the target structure, whose mechanism was investigated.

Photomagnetic effect in a cyanide-bridged mixed-valence {Fe(II)2Fe(III)2} molecular square.

The self-assembly of [Fe(III)(Tp)(CN)(3)](-) and [Fe(II)(bik)(2)(S)(2)](2+) affords the cyanide-bridged mixed valence {Fe(III)(2)Fe(II)(2)}(2+) molecular square, which exhibits a photomagnetic effect under laser light irradiation at low temperature and also shows thermal spin-state conversion near ambient temperature.

First example of an enantiopure planar chiral ligand built on a (eta5-cyclohexadienyl)Mn(CO)3 scaffold.

The synthesis of (eta5-cyclohexadienyl)Mn(CO)3-based planar chiral ligands is realized by an efficient lithiation/electrophilic quench procedure, and the coordinating properties of one of them are highlighted together with its optical resolution.

Further studies of the norditerpene (+)-harringtonolide isolated from Cephalotaxus harringtonia var. drupacea: absolute configuration, cytotoxic and antifungal activities.

Harringtonolide (= hainanolide) is a complex polycyclic fused norditerpene isolated from CEPHALOTAXUS HARRINGTONIA var. DRUPACEA. In spite of its appealing biological properties - we measured an IC (50) of 43 nM on KB cells and a significant antifungal activity - its absolute configuration has not yet been firmly established. This was done herein using X-ray anomalous scattering after bromination of the tropone ring, unambiguously giving the stereochemistry 5 R,6 R,7 S,13 S,14 S,15 R,16 R. Detailed IN VITRO biological measurements are provided.

Trapping of hemiquinone radicals at Mo and P sites by phosphide-bridged dimolybdenum species: chemistry of complexes [Mo2(eta5-C5H5)2(OC6H4OH)(mu-PR2)(CO)4] and [Mo2(eta5-C5H5)2{mu-PR(OC6H4OH)}(CO)4]- (R = Cy, Ph).

The phosphide-bridged dimolybdenum complexes (H-DBU)[Mo2Cp2(mu-PR2)(CO)4] (R= Cy, Ph; DBU = 1,8-diazabicyclo[5.4.0.]undec-7-ene) react with p-benzoquinone to give the hemiquinone complexes [Mo(2)Cp2(OC6H4OH)(mu-PR2)(CO)4]. The latter experience facile homolytic cleavage of the corresponding Mo-O bonds and react readily at room temperature with HSPh or S2Ph2 to give the thiolate complexes [Mo2Cp2(mu-PCy2)(mu-SPh)(CO)4] or [Mo2Cp2(mu-PR2)(mu-SPh)(CO)2]. In contrast, PRH-bridged substrates experience overall insertion of quinone into the P-H bond to give the anionic compounds (H-DBU)[Mo(2)Cp2{mu-PR(OC6H4OH)}(CO)4], which upon acidification yield the corresponding neutral hydrides. The cyclohexyl anion experiences rapid nucleophilic displacement of the hemiquinone group by different anions ER- (ER = OH, OMe, OC4H5, OPh, SPh) to give novel anionic compounds (H-DBU)[Mo2Cp2{mu-PCy(ER)}(CO)4], which upon acidification yield the corresponding neutral hydrides. The structure of four of these hydride complexes [PPh(OC6H4OH), PCy(OH), PCy(OMe), and PCy(OPh) bridges] was determined by X-ray diffraction methods and confirmed the presence of cis and trans isomers in several of these complexes. In addition, it was found that the hydroxyphosphide anion [Mo2Cp2{mu-PCy(OH)}(CO)4]- displays in solution an unprecedented tautomeric equilibrium with its hydride-oxophosphinidene isomer [Mo2Cp2(mu-H){mu-PCy(O)}(CO)4]-.

Zirconium-substituted isopolytungstates: structural models for zirconia-supported tungsten catalysts.

The synthesis and characterization of a series of mixed W-Zr polynuclear Lindqvist-type complexes, deriving from hexatungstate [W6O19]2-, are described in this work. This family of compounds is built from {W5O18Zr}2- moieties as shown by the X-ray structures of the monomeric [W5O18Zr(H2O)(3-n)(DMSO)n]2- (n = 1 and 2) and dimeric [{W5O18Zr(mu-OH)}2]6- anions. A comprehensive spectroscopic study (183W NMR, FTIR, Raman, EXAFS, and EPR) of these compounds is presented. The goal of incorporating Zr(IV) cations into an oxotungstic core is to obtain spectroscopic models that could mimic the interactions that develop in supported catalysts between the active phase and the supporting oxide. This work tends to show that these molecular compounds can be regarded as soluble structural analogues of WOx/ZrO2 catalysts, which are interesting candidates for the skeletal isomerization of light n-alkanes.

Mixed crystals containing the dioxo complex [[Ph3SiO]2VO2]- and novel pentacoordinated oxoperoxo complex [[Ph3SiO]2VO(O2)]-: X-ray crystal structure and assessment as oxidation catalysts.

[n-Bu4N][[Ph3SiO]2VO2] reacts with H2O2 to yield an oxoperoxo complex which crystallizes as a mixed-crystal compound, [P(C6H5)4][[(C6H5)3 SiO]2VO2]x[[(C6H5)3 SiO]2VO(O2)](1-x), 1(x = 0.57). It has been characterized by elemental analysis and spectroscopy (51V NMR, UV-visible and IR). The X-ray structure analysis reveals the presence of two interrelated anions: [[Ph3SiO]2VVO2]-, 1a, and [[Ph3SiO]2VVO(O2)]-, 1b with a cisoid geometry of the [VO(O2)]+ moiety. The two structures differ only slightly: anion 1a exhibits unusual tetrahedral coordination around the vanadium centre found in the precursor, whereas the geometry at the metal ion in 1b can be described as a trapezoidal pyramid. Steric constraints due to Ph3SiO- ligands and PPh4+ cations are responsible for this geometry. The reactivity of 1 in the C-C bond cleavage of 2-methylcyclohexanone under anaerobic conditions has been studied. The results suggest that peroxygen species are involved in the oxidative cleavage of C-C bonds of cycloalkanones.

Synthesis and characterization of the first carbene derivative of a polyoxometalate.

Reaction of the Keggin-type polyanion [PW11O39]7- with the tetrakis-carbene ruthenium precursor [RuLMe4Cl2] (LMe = 1,3-dimethylimidazolidine-2-ylidene), in water, results in the formation of Na4K9[(PW9O34)2(cis-WO2)(cis-RuLMe2)].23H2O, which is the first carbene derivative of a polyoxometalate. The oxidation state of the ruthenium is confirmed by XANES experiments.