RESUMEN
Reported herein is the synthesis of the previously unknown [Ir(1,5-COD)(µ-H)](4) (where 1,5-COD = 1,5-cyclooctadiene), from commercially available [Ir(1,5-COD)Cl](2) and LiBEt(3)H in the presence of excess 1,5-COD in 78% initial, and 55% recrystallized, yield plus its unequivocal characterization via single-crystal X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) spectroscopy, electrospray/atmospheric pressure chemical ionization mass spectrometry (ESI-MS), and UV-vis, IR, and nuclear magnetic resonance (NMR) spectroscopies. The resultant product parallels--but the successful synthesis is different from, vide infra--that of the known and valuable Rh congener precatalyst and synthon, [Rh(1,5-COD)(µ-H)](4). Extensive characterization reveals that a black crystal of [Ir(1,5-COD)(µ-H)](4) is composed of a distorted tetrahedral, D(2d) symmetry Ir(4) core with two long [2.90728(17) and 2.91138(17) Å] and four short Ir-Ir [2.78680 (12)-2.78798(12) Å] bond distances. One 1,5-COD and two edge-bridging hydrides are bound to each Ir atom; the Ir-H-Ir span the shorter Ir-Ir bond distances. XAFS provides excellent agreement with the XRD-obtained Ir(4)-core structure, results which provide both considerable confidence in the XAFS methodology and set the stage for future XAFS in applications employing this Ir(4)H(4) and related tetranuclear clusters. The [Ir(1,5-COD)(µ-H)](4) complex is of interest for at least five reasons, as detailed in the Conclusions section.
RESUMEN
A 1997 Nature paper (Nature 1997, 388, 353-355) and subsequent 1998 J. Am. Chem. Soc. paper (J. Am. Chem. Soc. 1998, 120, 11969-11976) reported that a putative Ru(2)-substituted polyoxoanion, "[WZnRu(2)(III)(H(2)O)(OH)(ZnW(9)O(34))(2)](11-)", (1), is an all inorganic dioxygenase able to incorporate one O(2) into two adamantane CH bonds to yield 2 equiv of 1-adamantanol as the primary product. In a subsequent 2005 Inorg. Chem. publication (Inorg. Chem. 2005, 44, 4175-4188), strong evidence was provided that the putative dioxygenase chemistry is, instead, the result of classic autoxidation catalysis. That research raised the question of whether the reported Ru(2) precatalyst, 1, was pure or even if it contained two Ru atoms, since Ru is known to be difficult to substitute into polyoxoanion structures (Nomiya, K.; Torii, H.; Nomura, K.; Sato, Y. J. Chem. Soc. Dalton Trans. 2001, 1506-1521). After our research group had contact with three other groups who also had difficulties reproducing the reported synthesis and composition of 1, we decided to re-examine 1 in some detail. Herein we provide evidence that the claimed 1 actually appears to be the parent polyoxoanion [WZn(3)(H(2)O)(2)(ZnW(9)O(34))(2)](12-) with small amounts of Ru (=0.2 atoms) either substituted into the parent complex or present as a small amount of a Ru(n+) impurity, at least in our and two other group's hands. The evidence obtained, on three independent samples prepared from two research groups including ours, includes elemental analysis on the bulk samples, single crystal X-ray diffraction, elemental analysis on single crystals from the same batch used for X-ray diffraction, (183)W NMR, and adamantane oxidation oxygen uptake and product determination studies. Also re-examined herein are the two previously reported crystal structures of 1 that appear to be very similar to the structure of the parent polyoxoanion, [WZn(3)(H(2)O)(2)(ZnW(9)O(34))(2)](12-). Furthermore, we report that trace Ru alone, in the form of [Ru(DMSO)(4)Cl(2)], or that the parent polyoxoanion [WZn(3)(H(2)O)(2)(ZnW(9)O(34))(2)](12-) alone, are capable of producing the same products. More significantly, a simple physical mixture of [WZn(3)(H(2)O)(2)(ZnW(9)O(34))(2)](12-) plus the average 0.13 equiv of Ru found by analysis added as the [Ru(DMSO)(4)Cl(2)] starting material is a ca. 2-fold kinetically more competent catalyst than is "[WZnRu(2)(III)(H(2)O)(OH)(ZnW(9)O(34))(2)](11-)", (1). In short, the evidence is strong that the putative "[WZnRu(2)(III)(H(2)O)(OH)(ZnW(9)O(34))(2)](11-)", (1), which underlies the previously reported all-inorganic dioxygenase catalysis claim, is probably not correct. That does not mean that 1 cannot or even does not exist, but just that (a) no reliable synthesis of it exists if it has actually been made before, and (b) that a simple mixture of the [Ru(DMSO)(4)Cl(2)] plus [WZn(3)(H(2)O)(2)(ZnW(9)O(34))(2)](12-) precursors gives about 2-fold faster catalysis of adamantane hydroxylation that occurs by, the evidence suggests, a radical-chain autoxidation mechanism rather than via the previously claimed, novel all-inorganic-based dioxygenase catalysis.
Asunto(s)
Dioxigenasas/química , Rutenio/química , Compuestos de Tungsteno/química , Catálisis , Estructura MolecularRESUMEN
Adding 1% of the metallic elements cerium, lanthanum, and yttrium to graphite rod electrodes resulted in different amounts of the hollow higher fullerenes (HHFs) C76-D2(1), C78-C2v(2), and C78-C2v(3) in carbon-arc fullerene-containing soots. The reaction of trifluoroiodomethane with these and other soluble HHFs at 520-550 degrees C produced 21 new C76,78,84,90(CF3)n derivatives (n = 6, 8, 10, 12, 14). The reaction with C76-D2(1) produced an abundant isomer of C2-(C76-D2(1))(CF3)10 plus smaller amounts of an isomer of C1-(C76-D2(1))(CF3)6, two isomers of C1-(C76-D2(1))(CF3)8, four isomers of C1-(C76-D2(1))(CF3)10, and one isomer of C2-(C76-D2(1))(CF3)12. The reaction with a mixture of C78-D3(1), C78-C2v(2), and C78-C2v(3) produced the previously reported isomer C1-(C78-C2v(3))(CF3)12 (characterized by X-ray crystallography in this work) and the following new compounds: C2-(C78-C2v(3))(CF3)8; C2-(C78-D3(1))(CF3)10 and C(s)-(C78-C2v(2))(CF3)10 (both characterized by X-ray crystallography in this work); C2-(C78-C2v(2))(CF3)10; and C1-C78(CF3)14 (cage isomer unknown). The reaction of a mixture of soluble higher fullerenes including C84 and C90 produced the new compounds C1-C84(CF3)10 (cage isomer unknown), C1-(C84-C2(11))(CF3)12 (X-ray structure reported recently), D2-(C84-D2(22))(CF3)12, C2-(C84-D2(22))(CF3)12, C1-C84(CF3)14 (cage isomer unknown), C1-(C90-C1(32))(CF3)12, and another isomer of C1-C90(CF3)12 (cage isomer unknown). All compounds were studied by mass spectrometry, (19)F NMR spectroscopy, and DFT calculations. An analysis of the addition patterns of these compounds and three other HHF(X) n compounds with bulky X groups has led to the discovery of the following addition-pattern principle for HHFs: In general, the most pyramidal cage C(sp(2)) atoms in the parent HHF, which form the most electron-rich and therefore the most reactive cage C-C bonds as far as 1,2-additions are concerned, are not the cage C atoms to which bulky substituents are added. Instead, ribbons of edge-sharing p-C6(X)2 hexagons, with X groups on less pyramidal cage C atoms, are formed, and the otherwise "most reactive" fullerene double bonds remain intact.
RESUMEN
The title compound, prepared from C(60) and CF(3)I at 500 degrees C, exhibits an unusual fullerene(X)12 addition pattern that is 40 kJ mol(-1) less stable than the previously reported C(60)(CF(3))12 isomer.
RESUMEN
The title compound, C(72)F(36), is one of four isomers of C(60)(CF(3))(12) for which crystal structures have been obtained. The fullerene mol-ecule has an idealized I(h) C(60) core with the 12 CF(3) groups arranged in an asymmetric fashion on two ribbons of edge-sharing C(6)(CF(3))(2) hexa-gons, a para-meta-para-para-para-meta-para ribbon and a para-meta-para ribbon, giving an overall pmp(3)mp,pmp structure. There are no cage Csp(3)-Csp(3) bonds. The F atoms of two CF(3) groups are disordered over two positions; the site occupancy factors are 0.85/0.15 and 0.73/0.27. There are intra-molecular Fâ¯F contacts between pairs of CF(3) groups on the same hexa-gon that range from 2.521â (3) to 2.738â (4)â Å.
RESUMEN
The high-temperature reaction of C60 and C2F5I produced poly(perfluoroethyl)fullerenes with unprecedented addition patterns.
RESUMEN
The dioxovanadium(IV) complexes with pida(4)(-) ligands (H(4)pida) = N-(phosphonomethyl)iminodiacetic acid), Na(4)[V(2)O(2){(O)(2)P(O)CH(2)N(CH(2)COO)(2)}(2)].10H(2)O (1) and Na(8)[V(2)O(2){(O)(2)P(O)CH(2)N(CH(2)COO)(2)}(2)](2).16H(2)O (2), were isolated from reactions of H(4)pida with either oxovanadium(V) (i.e., NaVO(3)) or oxovanadium(IV) precursors within the pH range of 2-8. The structures of complexes 1 and 2 were investigated by X-ray diffraction methods and in contrast to expectation were both found to be dinuclear. Complex 1 crystallized in the monoclinic system: P2(1)/n, a = 10.5632(1) Å, b = 11.1868(1) Å, c = 12.6921(1) Å, beta = 106.45 degrees, V = 1438.44(2) Å(3), Z = 4, and R (wR2) = 0.0781 (0.2017). Complex 2 crystallized in the monoclinic system P2(1)/c: a = 13.9822(2) Å, b = 11.1888(2) Å, c = 18.6519(3) Å, beta = 100.88 degrees, V = 2865.51(8) Å(3), Z = 4, and R (wR2) = 0.046 (0.125). Both complexes 1 and 2 have similar dimeric frameworks where two vanadium centers are linked by two phosphonate groups of two pida(4)(-) ligands (quadridentate binucleating), bridging through their four oxygen atoms to form a V(2)O(4)P(2) eight-membered ring which possesses a crystallographic inversion center. In contrast to their solid-state features, in aqueous solution both dinuclear crystalline compounds immediately dissociate to monomeric species, as observed by EPR and UV/vis spectroscopy. Both solution-state EPR and NMR spectroscopy confirmed that redox chemistry is involved in the reaction between vanadate and H(4)pida. Studies in mixed solvent systems showed that the dinuclear complex would remain intact in the presence of sufficient organic solvent. In the absence of oxygen the mononuclear and the dinuclear complexes will reversibly interconvert, whereas, in the presence of oxygen, the complexes will oxidize. These studies document the existence of higher oligomeric vanadium compounds and surprisingly, in general, lend credibility to several emerging mechanistic proposals involving oligomeric species of vanadium compounds in catalytic processes.
RESUMEN
The air-stable, free-radical, low-spin Co(III) complex, (Bu(4)N)(2) [3,5-Co(DBSQ)(CN)(4)].(1)/(2)H(2)O.(1)/(4)CH(2)Cl(2) (1), where 3,5-DBSQ is the semiquinone anion derived from the one-electron reduction of 3,5-di-tert-butyl-1,2-benzoquinone, has been synthesized by the reaction of the cobalt(II) tetramer [Co(3,5-DBSQ)(2)](4) with Bu(4)NCN in THF. This is a cyanide-induced redox reaction resulting in the formation of cobalt (II) and cobalt(III) products as follows, where 3,5-DBCat is the respective catecholate dianion: [Co(3,5-DBSQ)(2)](4) + 8CN(-) --> 2[Co(3,5-DBSQ)(CN)(4)](2)(-) + 2[Co(3,5-DBSQ)(2)(3,5-DBCat)](2)(-). The Co(III) product, (Bu(4)N)(2) [Co(3,5-DBSQ)(CN)(4)], is insoluble in THF while the Co(II) product remains in solution. Single-crystal X-ray diffraction of (1) reveals octahedrally coordinated cobalt(III) and C-O and C-C bond lengths indicative of semiquinone. The cyanide ligands occupy the remaining four sites with essentially linear Co-CN bond angles and average Co-C and Co-O bond distances of 1.89(2) Å and 1.97(2) Å, respectively. The complex has a magnetic moment of 1.80 &mgr;(B) and a typical semiquinone, S = (1)/(2), free-radical EPR signature (CH(2)Cl(2) solution, 293K) with g = 2.002, a(Co) = 8.8G, and a(H) = 2.6G. The identity of [Co(3,5-DBSQ)(2)(3,5-DBCat)](2)(-) (2) in the above reaction was confirmed by independent in situ generation of this anion from the reaction of [Co(3,5-DBSQ)(2)](4) with 3,5-DBCat(2)(-) solution.
RESUMEN
The studies of an underexplored synthetic reagent, VO(2)(acac) (Hacac = acetylacetone) and semirational strategies for the formation of a complete series of simple vanadium(V) alkoxide clusters in alcohol-containing solvents. The neutral mono-, di-, tri-, and tetranuclear oxovanadium(V) complexes [V(2)O(2)(&mgr;-OCH(3))(2)(acac)(2)(OCH(3))(2)] (1), [V(4)O(4)(&mgr;-O)(2)(&mgr;-OCH(3))(2)(&mgr;(3)-OCH(3))(2)(acac)(2)(OCH(3))(2)].2CH(3)CN (2), [V(4)O(4)(&mgr;-O)(2)(&mgr;-OCH(3))(2)(&mgr;(3)-OCH(3))(2)(acac)(2)(OCH(3))(2)] (3), [V(3)O(3){&mgr;,&mgr;-(OCH(2))(3)CCH(3)}(2)(acac)(2)(OR)] (R = CH(3) (4), C(2)H(5) (5)), and cis-[VO(OCH(CH(3))(2))(acac)(2)] (6) with alkoxide and acac(-) ligands were obtained by reaction of VO(2)(acac) with a monoalcohol and/or a tridentate alcohol. The structures of complexes 1-3, 5, and 6 were determined by X-ray diffraction methods. Complex 1 crystallized in the monoclinic system, P2(1)/n, with a = 7.8668(5) Å, b = 15.1037(9) Å, c = 8.5879(5) Å, beta = 106.150(1) degrees, V = 980.1(1) Å(3), Z = 2, and R (wR2) = 0.040 (0.121). Complex 2 crystallized in the monoclinic system, P2(1)/n, with a = 8.531(2) Å, b = 14.703(3) Å, c = 12.574(2) Å, beta = 95.95(2) degrees, V = 1568.7(5) Å(3), Z = 2, and R (wR2) = 0.052 (0.127). Complex 3 crystallized in the triclinic system, P&onemacr;, with a = 8.5100(8) Å, b = 8.9714(8) Å, c = 10.3708(10) Å, alpha = 110.761(1) degrees, beta = 103.104(1) degrees, gamma = 100.155(1) degrees, V = 691.85(11) Å(3), Z = 1, and R (wR2) = 0.040 (0.105). Complex 5 crystallized in the monoclinic system, P2(1)/n, with a = 14.019(2) Å, b = 11.171(2) Å, c = 19.447(3) Å, beta = 109.18(1) degrees, V = 2876.5(8) Å(3), Z = 4, and R (wR2) = 0.062 (0.157). Complex 6 crystallized in the monoclinic system, P2(1)/n, with a = 15.0023(8) Å, b = 8.1368(1) Å, c = 26.5598(2) Å, beta = 95.744(1) degrees, V = 3225.89(8) Å(3), Z = 8, and R (wR2) = 0.060 (0.154). Complex 1 is a discrete, centrosymmetric dimer in which two vanadium atoms are bridged by two methoxide ligands. Compound 2 contains a V(4)O(4) eight-membered ring with both &mgr;-oxo and &mgr;-alkoxo bridging ligands; the ring is capped above and below by two triply bridging methoxo ligands. Compound 3 has the same structure as 2. The three vanadium atoms in complex 5 are linked by four bridging oxygen atoms from two tridentate thme(3)(-) ligands to form a V(3)O(4) chain in which V-O bonds alternate in length. The V-O(isopropoxo) bond in 6 is cis to V=O, and the V-O(acac) bond trans to the oxo group is relatively long. The V(2)O(2) rings of complex 1 and the mononuclear 1:2 complex can be considered to be the basic building block of the trinuclear complexes 4 and 5 and the tetranuclear complex 2, acting to extend the vanadium-oxide framework. (51)V and (1)H NMR spectroscopic studies of the solution state of complexes 1-6 revealed dramatic differences in structural and hydrolytic stability of these complexes. Compounds 1 and 3 only remained intact at low temperature in CDCl(3) solution, whereas the mononuclear compound 6 could remain at ambient temperature for approximately 10 h. Compound 4 only maintained its solid-state structure at low temperature in CDCl(3) solution, whereas compound 5 was significantly more stable. The structural integrity of oligomeric vanadium-oxygen frameworks increased significantly when the coordinating alkoxide group showed more resistance to exchange reactions than the methoxide group. The solid state and solution properties of this new group of complexes not only testify to the versatility of VO(2)(acac) as a vanadium(V) precursor but also raise questions relating to solution structure and properties of related vanadium complexes with insulin-mimetic properties and catalytic properties.
RESUMEN
Tetranuclear vanadium complexes with alkoxy ligands, [V(4)O(4){&mgr;,&mgr;,&mgr;(3)-(OCH(2))(3)CCH(3)}(2)(OCH(3))(6)] (1) and [V(4)O(4){&mgr;-(OCH(2))(3)CCH(3)}{&mgr;,&mgr;(3)-(OCH(2))(3)CCH(3)}{&mgr;,&mgr;,&mgr;(3)-(OCH(2))(3)CCH(3)}(OR)(3)] (R = C(2)H(5) (2), R = CH(CH(3))(2) (3), R = CH(3) (4)), were synthesized by reacting VO(OR)(3) and H(3)thme (H(3)thme = 1,1,1-tris(hydroxymethyl)ethane) in alcohol. Complex 1 crystallized in the monoclinic space group P2(1)/n with a = 9.646(4) Å, b = 11.502(3) Å, c = 11.960(3) Å, beta = 90.20(3) degrees, V = 1326.9 (7) Å(3), Z = 2 and R (wR(2)) = 0.045 (0.143). Complex 2 also crystallized in the monoclinic space group P2(1)/n with a = 8.290(8) Å, b = 12.237(2) Å, c = 29.118(4) Å, beta = 89.455(9) degrees, V = 2954(3) Å(3), Z = 4, and R(wR(2)) = 0.049 (0.126). Both 1 and 2 are neutral, discrete complexes possessing a common [V(4)O(16)](12)(-) core, which consists of four vanadium(V) atoms chelated by two (1) or three (2) tridentate thme(3)(-) ligands and by six (1) or three (2) RO(-) groups. Compound 1 exhibits a crystallographically required inversion center; in contrast, complex 2 exhibits no crystallographically imposed symmetry, and its three trialkoxy ligands each coordinate differently (one thme(3)(-) is coordinated in a new coordination mode with the oxygens in a terminal, doubly-bridging and triply-bridging mode). Both compounds 1 and 2 maintain their structures in solution, although compound 1 also forms a second minor species upon dissolution. Sequential exchanges of the RO(-) groups in complexes 2 and 3 were investigated by (51)V and (1)H NMR spectroscopy. For example, [V(4)O(4)(thme)(3)(OC(2)H(5))(3)] will react with CH(3)OH to generate [V(4)O(4)(thme)(3)(OCH(3))(3)] (4). These reactions were found to be reversible. The time scale of the alcohol exchange reactions were found to vary depending on the vanadium center that is undergoing the exchange.
RESUMEN
A mononuclear vanadium(IV), a mononuclear vanadium(V), and a binuclear mixed valence vanadium(IV/V) complex with the ligand N-(2-hydroxyethyl)iminodiacetic acid (H(3)hida) have been structurally characterized. Crystal data for [VO(Hhida)(H(2)O)].CH(3)OH (1): orthorhombic; P2(1)2(1)2(1); a= 6.940(2), b = 9.745(3), c= 18.539(4) Å; Z = 4. Crystal data for Na[V(O)(2)(Hhida)(2)].4H(2)O (2): monoclinic; P2(1)/c; a = 6.333(2), b = 18.796(2), c = 11.5040(10) Å; beta = 102.53(2) degrees; Z = 4. Crystal data for (NH(4))[V(2)(O)(2)(&mgr;-O)(Hhida)(2)].H(2)O (3): monoclinic; C2/c; a = 18.880(2), b= 7.395(2), c = 16.010(2) Å; beta = 106.33(2) degrees; Z = 4. The mononuclear vanadium(IV) and vanadium(V) complexes are formed from the monoprotonated Hhida(2)(-) ligand, and their structural and magnetic characteristics are as expected for six-coordinate vanadium complexes. An interesting structural feature in these complexes is the fact that the two carboxylate moieties are coordinated trans to one another, whereas the carboxylate moieties are coordinated in a cis fashion in previously characterized complexes. The aqueous solution properties of the vanadium(IV) and -(V) complexes are consistent with their structures. The vanadium(V) complex was previously characterized; in the current study structural characterization in the solid state is provided. X-ray crystallography and magnetic methods show that the mixed valence complex contains two indistinguishable vanadium atoms; the thermal ellipsoid of the bridging oxygen atom suggests a type III complex in the solid state. Magnetic methods show that the mixed valence complex contains a free electron. Characterization of aqueous solutions of the mixed valence complex by UV/vis and EPR spectroscopies suggests that the complex may be described as a type II complex. The Hhida(2)(-) complexes have some similarities, but also some significant differences, with complexes of related ligands, such as nitrilotriacetate (nta), N-(2-pyridylmethyl)iminodiacetate (pmida), and N-(S)-[1-(2-pyridyl)ethyl]iminodiacetate (s-peida). Perhaps most importantly, the mixed valence Hhida(2)(-) complex is significantly less stable than the corresponding pmida and s-peida complexes of similar overall charge but very similar in stability to the nta and V(2)O(3)(3+) complexes with higher charges. Thus, there is the potential for designing stable mixed valence dimers.
RESUMEN
The effects of Mo-hydroxylamido complexes on cell growth were determined in Saccharomyces cerevisiae to investigate the biological effects of four different Mo complexes as a function of pH. Studies with yeast, an eukaryotic cell, are particularly suited to examine growth at different pH values because this organism grows well from pH 3 to 6.5. Studies can therefore be performed both in the presence of intact complexes and when the complexes have hydrolyzed to ligand and free metal ion. One of the complexes we examined was structurally characterized by X-ray crystallography. Yeast growth was inhibited in media solutions containing added Mo-dialkylhydroxylamido complexes at pH 3-7. When combining the yeast growth studies with a systematic study of the Mo-hydroxylamido complexes' stability as a function of pH and an examination of their speciation in yeast media, the effects of intact complexes can be distinguished from that of ligand and metal. This is possible because different effects are observed with complex present than when ligand or metal alone is present. At pH 3, the growth inhibition is attributed to the forms of molybdate ion that exist in solution because most of the complexes have hydrolyzed to oxomolybdate and ligand. The monoalkylhydroxylamine ligand inhibited yeast growth at pH 5, 6 and 7, while the dialkylhydroxylamine ligands had little effect on yeast growth. Growth inhibition of the Mo-dialkylhydroxylamido complexes is observed when a complex exists in the media. A complex that is inert to ligand exchange is not effective even at pH 3 where other Mo-hydroxylamido complexes show growth inhibition as molybdate. These results show that the formation of some Mo complexes can protect yeast from the growth inhibition observed when either the ligand or Mo salt alone are present.
Asunto(s)
Concentración de Iones de Hidrógeno , Hidroxilaminas/farmacología , Molibdeno/farmacología , Saccharomyces cerevisiae/efectos de los fármacos , Cristalografía por Rayos X , Medios de Cultivo , Electroquímica , Hidroxilaminas/química , Cinética , Modelos Moleculares , Conformación Molecular , Compuestos Organometálicos/química , Compuestos Organometálicos/farmacología , Saccharomyces cerevisiae/crecimiento & desarrolloRESUMEN
Three vanadium complexes of chlorodipicolinic acid (4-chloro-2,6-dipicolinic acid) in oxidation states III, IV, and V were prepared and their properties characterized across the oxidation states. In addition, the series of hydroxylamido, methylhydroxylamido, dimethylhydroxylamido, and diethylhydroxylamido complexes were prepared from the chlorodipicolinato dioxovanadium(V) complex. The vanadium(V) compounds were characterized in solution by (51)V and (1)H NMR and in the solid-state by X-ray diffraction and (51)V NMR. Density Functional Theory (DFT) calculations were performed to evaluate the experimental parameters and further describes the electronic structure of the complex. The small structural changes that do occur in bond lengths and angles and partial charges on different atoms are minor compared to the charge features that are responsible for the majority of the electric field gradient tensor. The EPR parameters of the vanadium(IV) complex were characterized and compared to the corresponding dipicolinate complex. The chemical properties of the chlorodipicolinate compounds are discussed and correlated with their insulin-enhancing activity in streptozoticin (STZ) induced diabetic Wistar rats. The effect of the chloro-substitution on lowering diabetic hyperglycemia was evaluated and differences were found depending on the compounds oxidation state similar as was observed for the vanadium III, IV and V dipicolinate complexes (P. Buglyo, D.C. Crans, E.M. Nagy, R.L. Lindo, L. Yang, J.J. Smee, W. Jin, L.-H. Chi, M.E. Godzala III, G.R. Willsky, Inorg. Chem. 44 (2005) 5416-5427). However, a linear correlation of oxidation states with efficacy was not observed, which suggests that the differences in mode of action are not simply an issue of redox equivalents. Importantly, our results contrast the previous observation with the vanadium-picolinate complexes, where the halogen substituents increased the insulin-enhancing properties of the complex (T. Takino, H. Yasui, A. Yoshitake, Y. Hamajima, R. Matsushita, J. Takada, H. Sakurai, J. Biol. Inorg. Chem. 6 (2001) 133-142).
Asunto(s)
Hipoglucemiantes/química , Insulina/farmacología , Ácidos Picolínicos/química , Compuestos de Vanadio/química , Animales , Diabetes Mellitus Experimental/tratamiento farmacológico , Espectroscopía de Resonancia por Spin del Electrón , Hipoglucemiantes/farmacología , Insulina/metabolismo , Espectroscopía de Resonancia Magnética , Oxidación-Reducción , Ácidos Picolínicos/farmacología , Ratas , Ratas Wistar , Compuestos de Vanadio/farmacologíaRESUMEN
The selective substitution of the antipodal F atom in 1-Me-CB(11)F(11)- with a SiPh(3) moiety led to the isolation and structure determination of the cesium(I) and silver(I) salts of the 1-Me-12-SiPh(3)-CB(11)F(10)- anion. The silver salt contains both a nearly trigonal-planar Ag(arene)(3)+ cation and the first example of a Ag(arene)(4)+ cation.
RESUMEN
A number of 4-substituted, dipicolinatodioxovanadium(V) complexes and their hydroxylamido derivatives were synthesized to characterize the solid state and solution properties of five- and seven-coordinate vanadium(V) complexes. The X-ray crystal structures of Na[VO2dipic-NH2].2H2O (2) and K[VO2dipic-NO2] (3) show the vanadium adopting a distorted, trigonal-bipyramidal coordination environment similar to the parent coordination complex, [VO2dipic]- (1), reported previously as the Cs+ salt. The observed differences in the chemical shifts of the complexes both in the 1H (ca. 0.7-1.4 ppm) and 51V (ca. 1-11 ppm) NMR spectra were consistent with the electron-donating or electron-withdrawing properties of the substituent groups, respectively. Stoichiometric addition of a series of hydroxylamine ligands (H2NOH, MeHNOH, Me2NOH, and Et2NOH) to complexes 1-3 led to the formation of seven-coordinate vanadium(V) complexes. The X-ray crystal structure of [VO(dipic)(Me2NO)(H2O)].0.5H2O (1c) was found to be similar to the previously characterized complexes [VO(dipic)(H2NO)(H2O)] (1a) and [VO(dipic)(OO-tBu)(H2O)]. While only slight differences in the 1H NMR spectra were observed upon addition of the hydroxylamido ligand, the signals in the 51V NMR spectra change by up to 100 ppm. The addition of the hydroxylamido ligand increased the complex stability of complexes 2 and 3. Evidence for a nonstoichiometric redox reaction was found for the monoalkyl hydroxylamine ligand. The reaction of an unsaturated five-coordinate species with a hydroxylamine to form a seven-coordinate vanadium complex will, in general, dramatically increase the amounts of the vanadium compound that remain intact at pH values near neutral.