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PubMed2006

Removing the sting from the tail: reversible protonation of scorpionate ligands in cobalt(II) tris(carbene)borate complexes.

Low-temperature deprotonation of the phenylborane dications, PhB(RIm)3OTf2 (R = tBu, Mes), followed by in situ reaction with CoCl2(thf)1.5, results in the formation of the four-coordinate complexes, kappa3-PhB(RIm)3CoCl, in which the metal is supported by tripodal N-heterocyclic carbene-based ligands. The chloride complexes are exceptionally sensitive to acid and can be reversibly protonated to form the zwitterions kappa2-{PhB(RIm)2(RIm.H)}CoCl2. This unexpected reactivity is attributed to the highly basic nature of the tris(carbene)borate ligands. Reaction of the chloride complexes with methylating reagents results in products that depend on the N-heterocyclic carbene substituent. For R = tBu, the four-coordinate high-spin complex, kappa3-PhB(tBuIm)3CoMe, is formed, while for R = Mes, reduction to a multitude of complexes occurs.

Boronic Acids↗

PubMed1996

Synthesis and Molecular Structures of Hydrotris(dimethylpyrazolyl)borate Complexes of the Lanthanides.

The reaction of lanthanide triflates with 2 equiv of potassium hydrotris(dimethylpyrazolyl)borate (Tp(Me)()2) gives good yields of complexes of composition Ln(Tp(Me)()2)(2)OTf. For La (2), Ce (3), Pr (4), and Nd (5) the complexes are seven-coordinate in the solid state with the triflate group coordinated to the metal in unidentate fashion. Complex 5 crystallizes in the monoclinic space group P2(1)/c with a = 17.629(3) Å, b = 12.740(2) Å, c = 18.163(3) Å, beta = 107.35(1) degrees, V = 3893(1) Å(3), Z = 4, and R(w) = 0.0458. For the complexes of Y (1), Sm (6), Eu (7), Gd (8), Dy (9), Ho (10), and Yb (11), the smaller size of the metal ion leads to ejection of the triflate from the coordination sphere and the complexes are ionic in the solid state with a six-coordinate metal center. Complex 11 crystallizes in the monoclinic space group C2/m with a = 16.593(7) Å, b = 13.671(5) Å, c = 8.746(2) Å, beta = 91.66(3) degrees, V = 1983(1) Å(3), Z = 2, and R(w) = 0.0416. In solution, however, complex 6 adopts a seven-coordinate molecular structure with the triflate ion within the first coordination sphere.

Journal Article↗

PubMed1996

Nature of the Rh-H(2) Bond in a Dihydrogen Complex Stabilized Only by Nitrogen Donors. Inelastic Neutron Scattering Study of Tp(Me)2RhH(2)(eta(2)-H(2)) (Tp(Me)2 = Hydrotris(3,5-dimethylpyrazolyl)borate).

The tunnel splitting of the librational ground state and the torsional frequencies of the dihydrogen ligand in Tp(Me)()2RhH(2)(eta(2)-H(2)) (Tp(Me)()2 = hydrotris(3,5-dimethylpyrazolyl)borate) were measured using inelastic neutron scattering spectroscopy. The barrier for the rotation of the H(2) ligand and its H-H separation, calculated from these data, are 0.56(2) kcal/mol and 0.94 Å, respectively. These values indicate that pi-back-donation from the Tp(Me)()2RhH(2) fragment to H(2) is relatively weak and/or the interaction between the coordinated dihydrogen molecule and the two cis-hydride ligands significantly lowers the barrier for H(2) rotation.

Journal Article↗

PubMed1996

Polyfluorinated Tris(pyrazolyl)borates. Syntheses and Spectroscopic and Structural Characterization of Group 1 and Group 11 Metal Complexes of [HB(3,5-(CF(3))(2)Pz)(3)](-) and [HB(3-(CF(3))Pz)(3)](-).

The fluorinated tris(pyrazolyl)borate ligands [HB(3,5-(CF(3))(2)Pz)(3)](-) and [HB(3-(CF(3))Pz)(3)](-) (where Pz = pyrazolyl) have been synthesized as their sodium salts from the corresponding pyrazoles and NaBH(4) in high yield. These sodium complexes and the related [HB(3,5-(CF(3))(2)Pz)(3)]K(DMAC) were used as ligand transfer agents in the preparation of the copper and silver complexes [HB(3,5-(CF(3))(2)Pz)(3)]Cu(DMAC), [HB(3,5-(CF(3))(2)Pz)(3)]CuPPh(3), [HB(3,5-(CF(3))(2)Pz)(3)]AgPPh(3), and [HB(3-(CF(3))Pz)(3)]AgPPh(3). Metal complexes of the fluorinated [HB(3,5-(CF(3))(2)Pz)(3)](-) ligand have highly electrophilic metal sites relative to their hydrocarbon analogs. This is evident from the formation of stable adducts with neutral oxygen donors such as H(2)O, dimethylacetamide, or thf. Furthermore, the metal compounds derived from fluorinated ligands show fairly long-range coupling between fluorines of the trifluoromethyl groups and the hydrogen, silver, or phosphorus. The solid state structures show that the fluorines are in close proximity to these nuclei, thus suggesting a possible through-space coupling mechanism. Crystal structures of the sodium adducts exhibit significant metal-fluorine interactions. The treatment of [HB(3,5-(CF(3))(2)Pz)(3)]Na(H(2)O) with Et(4)NBr led to [Et(4)N][HB(3,5-(CF(3))(2)Pz)(3)], which contains a well-separated [Et(4)N](+) cation and the [HB(3,5-(CF(3))(2)Pz)(3)](-) anion in the solid state. Crystal data with Mo Kalpha (lambda = 0.710 73 Å) at 193 K: [HB(3,5-(CF(3))(2)Pz)(3)]Na(H(2)O), C(15)H(6)BF(18)N(6)NaO, a = 7.992(2) Å, b = 15.049(2) Å, c = 9.934(2) Å, beta = 101.16(2) degrees, monoclinic, P2(1)/m, Z = 2; [{HB(3-(CF(3))Pz)(3)}Na(thf)](2), C(32)H(30)B(2)F(18)N(12)Na(2)O(2), a = 9.063(3) Å, b = 10.183(2) Å, c = 12.129(2) Å, alpha = 94.61(1) degrees, beta = 101.16(2) degrees, gamma = 95.66(2) degrees, triclinic, &Pmacr;1, Z = 1; [HB(3,5-(CF(3))(2)Pz)(3)]Cu(DMAC), C(19)H(13)BCuF(18)N(7)O, a = 15.124(4) Å, b = 8.833(2) Å, c = 21.637(6) Å, beta = 105.291(14) degrees, monoclinic, P2(1)/n, Z = 4; [HB(3,5-(CF(3))(2)Pz)(3)]CuPPh(3), C(33)H(19)BCuF(18)N(6)P, a = 9.1671(8) Å, b = 14.908(2) Å, c = 26.764(3) Å, beta = 94.891(1) degrees, monoclinic, P2(1)/c, Z = 4; [HB(3,5-(CF(3))(2)Pz)(3)]AgPPh(3).0.5C(6)H(14), C(36)H(26)AgBF(18)N(6)P, a = 13.929(2) Å, b = 16.498(2) Å, c = 18.752(2) Å, beta = 111.439(6) degrees, monoclinic, P2(1)/c, Z = 4; [Et(4)N][HB(3,5-(CF(3))(2)Pz)(3)], C(23)H(24)BF(18)N(7), a = 10.155(2) Å, b = 18.580(4) Å, c = 16.875(5) Å, beta = 99.01(2) degrees, monoclinic, P2(1)/n, Z = 4.

Journal Article↗

PubMed1997

Synthesis and Characterization of the Benzoylformato Ferrous Complexes with the Hindered Tris(pyrazolyl)borate Ligand as a Structural Model for Mononuclear Non-Heme Iron Enzymes.

By using a hindered tripodal ligand, hydrotris(3-tert-butyl-5-isopropylpyrazol-1-yl)borate HB(3-tBu-5-iPrpz)(3), a series of monomeric ferrous complexes having acetate, hydroxide, and benzoylformate ligands were synthesized. Reaction of KHB(3-tBu-5-iPrpz)(3) with anhydrous Fe(OAc)(2) yielded acetato complexes Fe(OAc)[HB(3-tBu-5-iPrpz)(3)] (1) and Fe(OAc)[HB(3-tBu-5-iPrpz)(3)](3-iPr-5-tBupzH) (2). A hydroxo complex Fe(OH)[HB(3-tBu-5-iPrpz)(3)] (3) was prepared by the treatment of 1 or 2 with aqueous NaOH. The geometry of Fe(II) in 3 is a slightly distorted tetrahedron as determined by X-ray crystallography. The hydroxo complex 3 reacted with benzoylformic acid to give the benzoylformato complex Fe(O(2)CC(O)Ph)[HB(3-tBu-5-iPrpz)(3)] (4), which showed thermochromism which depended on the coordination geometry of the benzoylformate ligand. The Fe(II) ion in the colorless form of 4 isolated at 4 degrees C is coordinated by a tetrahedral N(3)O(1) ligand donor set including the unidentate benzoylformato ligand. On the other hand, the bluish purple form of 4 isolated at -20 degrees C has a five-coordinate trigonal bipyramidal Fe(II) center. The benzoylformate ligand in this bluish purple form works as a chelate ligand through coordination of the unidentate carboxylate oxygen atom as well as the ketonic oxygen atom. A benzoylformato complex containing an additional pyrazole, Fe(O(2)CC(O)Ph)[HB(3-tBu-5-iPrpz)(3)](3-iPr-5-tBupzH) (5), was obtained by the reaction of 3 with benzoylformic acid in the presence of 3-tert-butyl-5-isopropylpyrazole. The iron atom in 5 is coordinated by an N(4)O(1) ligand donor set with trigonal bipyramidal geometry. A hydrogen-bonding interaction between the carboxylate oxygen atom and the additional pyrazole's NH proton in 5 is suggested from the short distance between O(carboxylate) and N(pyrazole) observed in the X-ray structure and the absence of the nuNH vibration in the IR spectrum.

Journal Article↗

PubMed1997

Vanadium Hydrotris(pyrazolyl)borate Complexes of Diphenyl Phosphate. Heterometallic Complexes of the [LV{(PhO)(2)PO(2)}(3)](-) Fragment.

The synthesis and characterization of nine trinuclear, mixed metal complexes of the type [LV{&mgr;-(PhO)(2)PO(2)}(3)](2)M, where the vanadium is in the 3+ oxidation state, L = hydrotris(pyrazolyl)borate, and M = Ba(II) (1), Ca(II) (2), Mg(II) (3), Mn(II) (4), Co(II) (5), Ni(II) (6), Fe(II) (7), 2 Na(I) (8), Al(III) (9), and La(III) (10), are described. X-ray crystal structural analysis of 1, 3, and 4 gave the following parameters: 1, C(92)H(84)B(2)N(12)O(24)P(6)Cl(4)BaV(2), C2/c, a = 26.730(5) Å, b = 15.521(3) Å, c = 27.648(6) Å, beta = 100.53(3) degrees, Z = 4; 3, C(94)H(80)B(2)N(14)O(24)P(6)MgV(2), P&onemacr;, a = 13.410(3) Å, b = 14.179(3) Å, c = 15.694(3) Å, alpha = 112.22(3) degrees, beta = 101.31(3) degrees, gamma = 106.15(3) degrees, Z = 1; 4, C(111)H(80)B(2)N(12)O(28)P(6)MnV(2), R&thremacr;c, a = 18.670(3) Å, b = 18.671(3) Å, c = 61.114(12) Å, Z = 6. Magnetic measurements indicate that compounds containing an integral spin central ion display moderate antiferromagnetic coupling while those with half-integral spins give more complex behavior.

Journal Article↗

PubMed1997

Ferrocene-Based Tris(1-pyrazolyl)borates: A New Approach to Heterooligometallic Complexes and Organometallic Polymers Containing Transition Metal Atoms in the Backbone.

Starting from mono- and bifunctional ferrocene-based tris(1-pyrazolyl)borates, a novel route to oligonuclear complexes is presented, which incorporates transition metal centers differing substantially in their chemical nature. Both binuclear organometallics FcB(pz)(3)ML(n)() (Fc: ferrocenyl. pz: 1-pyrazolyl. ML(n)(): Tl, 1-Tl; Mo(CO)(3)Li, 1-MoLi; Mo(CO)(2)(eta(3)-methylallyl), 1-Mo; ZrCl(3), 1-Zr) and trinuclear complexes 1,1'-fc[B(pz)(3)ML(n)()](2) (fc: ferrocenylene. ML(n)(): Tl, 2-Tl; Mo(CO)(3)Li, 2-MoLi; Mo(CO)(2)(eta(3)-methylallyl), 2-Mo) have been prepared. The trinuclear compound [FcB(4-SiMe(3)pz)(3)](2)Fe, 1-FeSi, has been investigated as a model system for organometallic coordination polymers, consisting of the bifunctional linker 1,1'-fc[B(pz)(3)](2)(2)(-) and transition metal ions M(n)()(+). X-ray crystallography shows 1-Tl to establish a polymeric structure in the solid state, while 1-Mo features the usual tridentate coordination mode of the scorpionate ligand (C(25)H(25)BFeMoN(6)O(2); a = 8.756(1) Å, b = 12.154(1) Å, c = 12.927(1) Å, alpha = 105.26(1) degrees, beta = 102.29(1) degrees, gamma = 105.09(1) degrees; triclinic space group P&onemacr;; Z = 2). With the exception of 1,2-Tl, the anodic oxidation of the ferrocene moiety is generally reversible; cyclic voltammetry measurements indicate the two Mo centers in 2-Mo and the two Fc moieties in 1-FeSi to be noncommunicating.

Journal Article↗

PubMed1997

Cobalt as a Probe for Zinc in Metalloenzyme Model Compounds? A Comparison of Spectroscopic Features and Coordination Geometry of Four- and Five-Coordinate Complexes. Crystal and Molecular Structures of [Co(eta(3)-Tp(Ph))(eta(2)-Tp(Ph))], [(eta(3)-Tp(Ph))Zn(anthranilate)], and [(eta(3)-Tp(Ph))M(eta(2)-acac)] (Tp(Ph) = Hydrotris(3-phenylpyrazol-1-yl)borate, acac = Pentane-2,4-dionate, and M = Zn, Co).

The reaction of cobalt(II) perchlorate with 1 equiv each of potassium hydroxide and potassium hydrotris(3-phenylpyrazolyl)borate (KTp(Ph)) leads to the formation of the blood-red bis(ligand) complex [Co(eta(3)-Tp(Ph))(eta(2)-Tp(Ph))]. This compound crystallizes in the monoclinic space group P2(1)/n, with a = 10.690(5) Å, b = 34.243(15) Å, c = 12.923(4) Å, beta = 96.17(3) degrees, Z = 4, V = 4703(3) Å(3), and R = 0.040. The molecular structure contains a square CoN(5) pyramid with an agostic BH.Co interaction of 2.17(2) Å. One Tp(Ph) ligand acts tridentate; the other, bidentate. The reaction of KTp(Ph) with zinc and cobalt halides yields a series of heteroleptic halogeno complexes [(Tp(Ph))MX]. The zinc species are all tetrahedral, while in the case of cobalt(II) the UV-vis spectra indicate an equilibrium of tetra- and pentacoordinated species depending on the anion size and the donor properties of the solvent. Metathesis reactions with carboxylates yield mononuclear complexes [(Tp(Ph))M(O(2)CR)]; M = Zn(II), Co(II); RCO(2)(-) = acetate, benzoate, 4-fluorobenzoate, and 4-nitrobenzoate. The infrared bands nu(as)(CO(2)) and nu(sym)(CO(2)) indicate monodentate carboxylate ligands in the zinc complexes in the solid state and in solution. The cobalt complexes [(Tp(Ph))Co(carboxylate)] are dark blue in dichloromethane and in the solid state when grown from dichloromethane solution. Tetrahydrofuran solutions and crystals grown from tetrahydrofuran are pink, purple, or reddish violet. The 2-aminobenzoate (anthranilate) complexes [(Th(Ph))M(anthranilate)], M = Zn(II), Co(II), have been prepared. [(eta(3)-Tp(Ph))Zn(anthranilate)] crystallizes in the monoclinic space group P2(1)/n, with a = 13.205(4) Å, b = 15.643(3) Å, c = 15.116(3) Å, beta = 98.86(2) degrees, Z = 4, V = 3085(1) Å(3), and R = 0.034. Anthranilate acts as a chelating oxygen ligand with Zn-O distances of 1.932(2) and 2.460(2) Å. The amino group is not involved in metal coordination. The reaction of the chloro complexes [(Tp(Ph))MCl] with sodium or potassium acetylacetonate leads to isotypic zinc and cobalt complexes [(eta(3)-Tp(Ph))M(eta(2)-acac)]. Both crystallize in the monoclinic space group P2(1)/c, with Z = 4, the zinc compound with a = 16.334(3) Å, b = 11.545(2) Å, c = 15.816(3) Å, beta = 94.77(1) degrees, V = 2972(1) Å(3), and R = 0.039 and the cobalt compound with a = 16.358(7) Å, b = 11.519(2) Å, c = 15.847(6) Å, beta = 95.30(3) degrees, V = 2973(2) Å(3), and R = 0.035. The structures are best described as slightly distorted trigonal bipyramids with the two axial positions occupied by one of the acetylacetonate O and one of the tripodal N donor atoms. Ligand profiles of Tp(Ph) and related ligands have been calculated to visualize the angular encumbrance of the ligands.

Journal Article↗

PubMed1997

Pocket Semiquinonate Complexes of Cobalt(II), Copper(II), and Zinc(II) Prepared with the Hydrotris(cumenylmethylpyrazolyl)borate Ligand.

3,5-Di-tert-butyl-1,2-semiquinonate (3,5-DBSQ) complexes of Co(II), Cu(II), and Zn(II) have been prepared that contain the hydrotris(cumenylmethyl-pyrazolyl)borate (Tp(Cum,Me)) coligand. Tp(Cum,Me)Zn(3,5-DBSQ) and Tp(Cum,Me)Cu(3,5-DBSQ) were prepared by treating the parent hydroxide, Tp(Cum,Me)M(OH), M = Cu and Zn, with 3,5-di-tert-butylcatechol. Tp(Cum,Me)Co(3,5-DBSQ) was prepared by a reaction between (Tp(Cum,Me))(2)Co and 3,5-DBCat. The identity of (Tp(Cum,Me))(2)Co in this reaction was confirmed by a structure determination [(Tp(Cum,Me))(2)Co: orthorhombic, Pbcn, a = 17.7189(4) Å, b = 17.4806(3) Å, c = 25.7123(6) Å, V = 7964.1(3) Å(3), Z = 4, R(F) = 0.054]. Intersecting cumenyl substituents of the pyrazolylborate ligand encapsulate the Co(II) ion. Structural characterization on all three members of the Tp(Cum,Me)M(3,5-DBSQ) series has been carried out. The complexes of Co(II) and Zn(II) are isomorphous and isostructural [Tp(Cum,Me)Co(3,5-DBSQ): triclinic, P&onemacr;, a = 14.4631(2) Å, b = 18.5438(3) Å, c = 21.6142(2) Å, alpha = 79.8430(10) degrees, beta = 90.0900(10) degrees, gamma = 84.9900(10) degrees, V = 5683.45(13) Å(3), Z = 4, R(F) = 0.072; Tp(Cum,Me)Zn(3,5-DBSQ), triclinic, P&onemacr;, a = 14.261(3) Å, b = 18.760(7) Å, c = 21.710(4) Å, alpha = 80.049(12) degrees, beta = 89.853(8) degrees, gamma = 85.542(12) degrees, V = 5703(3) Å(3), Z = 4, R(F) = 0.064]. Tp(Cum,Me)Cu(3,5-DBSQ) [monoclinic, P2(1)/c, a = 19.3081(3) Å, b = 13.0291(2) Å, c = 21.4783(4) Å, beta = 102.8420(10) degrees, V = 5268.1(2) Å(3), Z = 4, R(F) = 0.071] has a distorted square pyramidal structure, the complexes of Zn and Co have structures that are closer to a trigonal bipyramid. Parent catecholate complexes of all three metals are unusually stable in air but undergo slow oxidation in solution to give the semiquinonate products characterized structurally. Copper(II) and SQ spins of Tp(Cum,Me)Cu(3,5-DBSQ) are located in orthogonal orbitals, and the complex has a S = 1 spin state. The charge distribution in Tp(Cum,Me)Co(3,5-DBSQ) is Co(II)-SQ, rather than the more common Co(III)-Cat, due to surprisingly weak donation by the Tp(Cum,Me) nitrogens.

Journal Article↗

PubMed1998

Chelated Borates: Synthesis, Reactivity, and Cation Formation.

The ligands N-salicylidene-o-aminophenol (LH(2)), N-(5-chlorosalicylidene)-o-aminophenol (L(Cl)H(2)), and N-(5-bromosalicylidene)-o-aminophenol (L(Br)H(2)) were used to prepare a series of borates having the formulas LBOR (R = Me (1), Et (2), (n)Pr (3), (n)Bu (4)), L(Cl)BOR (R = Me (5), Et (6), (n)Pr (7), (n)Bu (8)), and L(Br)BOR (R = Me (9), Et (10), (n)Pr (11), (n)Bu (12)). Either 1-4 or 9-12 could be combined with HOSiPh(3), to form unique compounds possessing a single B-O-Si linkage, LBOSiPh(3) (13) and L(Br)BOSiPh(3) (14), respectively. The charged species, [LB(thf)](+)OTf(-) (15) forms when 1 is combined with HOTf. It can be used as a catalyst for the oligomerization of propylene oxide. By comparison, [(n)Bu(2)B](+)OTf(-) effects the oligomerization to the same extent as 15, but the neutral species, 1-4, 13, and 14 do not, even under forcing conditions. All of the compounds were characterized by melting point, (1)H NMR, IR, elemental analyses, and, in the case of 13, by X-ray crystallography.

Journal Article↗

PubMed2000

Low-valent gallium, indium, and tin compounds that contain a highly fluorinated tris(pyrazolyl)borate ligand: syntheses and characterization of.

Syntheses and characterization of gallium(I), indium(I), and tin(II) complexes of the [HB(3,5-(CF3)2Pz)3]- ligand (where [HB(3,5-(CF3)2Pz)3]- = hydrotris(3,5-bis(trifluoromethyl)pyrazolyl)borate)) are reported. X-ray crystal structures of [HB(3,5-(CF3)2Pz)3]In and [HB(3,5-(CF3)2Pz)3]Sn(CF3SO3) show monomeric structures in the solid state. The In-N and Sn-N bond distances are longer than the corresponding bond distances of nonfluorinated analogues. NMR data of the gallium(I) adduct [HB(3,5-(CF3)2Pz)3]Ga are very similar to those of the indium(I) analogue suggesting similar solution structures.

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PubMed2002

Structure and ion exchange properties of a new cobalt borate with a tunnel structure "templated" by Na+.

The new anhydrous borate Na2Co2B12O21 has been synthesized by flux methods and studied by single-crystal X-ray diffraction (space group I2/a with a = 17.1447(15) A, b = 4.5530(5) A, c = 19.4408(15) A, beta = 103.212(5) degrees , V = 1477.4(2) A3, Z = 4). Refinement of its structure reveals it is the first metaborate exhibiting a tunnel network, with internal dimensions of 4.5 x 8.8 A2. Further single-crystal diffraction studies show that the Na+ ions within the tunnels are exchangeable with Li+ along with the absorption of water molecules to form Li2(H2O)2Co2B12O21, making this compound a unique non-siliceous zeotype.

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PubMed2004

Direct access to ketones from aldehydes via rhodium-catalyzed cross-coupling reaction with potassium trifluoro(organo)borates.

A direct cross-coupling reaction of aromatic aldehydes with potassium trifluoro(organo)borates afforded ketones in high yields and under mild conditions in the presence of a rhodium catalyst and acetone. This new reaction, involving a formal aldehyde C-H bond activation, is believed to proceed via a Heck-type mechanism followed by hydride transfer to acetone.

Journal Article↗

PubMed2005

Formation of third generation poly(pyrazolyl)borate ligands from alkyne coupling reactions of Fe[(p-IC6H4)B(3-Rpz)3]2 (R = H, Me; pz = pyrazolyl): pathways toward controlling an iron(II) electronic spin-state crossover.

Sonogashira coupling reactions of terminal alkynes with Fe[(p-IC6H4)B(3-Mepz)3]2 (pz = pyrazolyl ring) yield Fe[(p-PhC2C6H4)B(3-Mepz)3]2 (2), Fe[(p-Me3SiC2C6H4)B(3-Rpz)3]2 (R = H, 3a, R = Me, 3b), and Fe[(p-HC2C6H4)B(3-Mepz)3]2 (R = H, 4a, R = Me, 4b), a series of new complexes containing "third generation" poly(pyrazolyl)borate ligands. Complex 2 undergoes a fairly gradual iron(II) electronic spin-state crossover with a 30 K hysteresis, whereas complex 3b is an unusual example of a complex with equivalent iron(II) sites in the high-spin form that shows an abrupt 50% spin crossover. For complex 4b, 50% of the iron(II) sites undergo a gradual spin-state transition between 185 and 350 K with an activation energy of 1590 +/- 30 cm(-1) and a T(1/2) = 280 K and, for the remaining iron(II) sites, an abrupt cooperative spin-state crossover between 106 and 114 K. The crystal structures of 4b obtained for each of the three distinct electronic spin states reveal two crystallographically different iron(II) sites, and analysis of the molecular/supramolecular structures indicates that the difference in the degree of pyrazolyl ring tilting in the ligands between the two sites, rather than the strength of the intermolecular forces, play a prominent role in determining the temperature of the spin-state crossover.

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PubMed2005

Unusual reactivity of tris(pyrazolyl)borate zirconium benzyl complexes.

The synthesis and reactivity of [Tp*Zr(CH2Ph)2][B(C6F5)4] (2, Tp* = HB(3,5-Me2pz)3, pz = pyrazolyl) have been explored to probe the possible role of Tp'MR2+ species in group 4 metal Tp'MCl3/MAO olefin polymerization catalysts (Tp' = generic tris(pyrazolyl)borate). The reaction of Tp*Zr(CH2Ph)3 (1) with [Ph3C][B(C6F5)4] in CD2Cl2 at -60 degrees C yields 2. 2 rearranges rapidly to [{(PhCH2)(H)B(mu-Me2pz)2}Zr(eta2-Me2pz)(CH2Ph)][B(C6F5)4] (3) at 0 degrees C. Both 2 and 3 are highly active for ethylene polymerization and alkyne insertion. Reaction of 2 with excess 2-butyne yields the double insertion product [Tp*Zr(CH2Ph)(CMe=CMeCMe=CMeCH2Ph)][B(C6F5)4] (4). Reaction of 3 with excess 2-butyne yields [{(PhCH2)(H)B(mu-Me2pz)2}Zr(Cp*)(eta2-Me2pz)][B(C6F5)4] (6, Cp* = C5Me5) via three successive 2-butyne insertions, intramolecular insertion, chain walking, and beta-Cp* elimination.

Journal Article↗

PubMed2005

Palladium pincer complex catalyzed substitution of vinyl cyclopropanes, vinyl aziridines, and allyl acetates with tetrahydroxydiboron. An efficient route to functionalized allylboronic acids and potassium trifluoro(allyl)borates.

Palladium-catalyzed boronation of vinyl cyclopropane, vinyl aziridine, and allyl acetate substrates could be accomplished using tetrahydroxydiboron reagent in the presence of SeCSe pincer complex catalyst 1a. These reactions result in allyl boronic acids, which were converted to synthetically useful trifluoro(allyl)borates or allyl boronates. The catalytic transformations proceed under mild and neutral conditions, and therefore many functionalities Br, COOEt, ArSO2(NH), OAc, and SiRMe2 are tolerated. The selectivity of the presented processes is very high, affording the linear products incorporating a trans double bond.

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PubMed2006

UV-induced nonlinear absorption in lanthanum calcium borate single crystals.

It has been revealed that lanthanum calcium borate (La2CaB10O19) crystals show two-photon absorption (TPA) induced by a UV laser field. UV-induced TPA measurements were performed in the spectral range of 475-1130 nm using as fundamental beam the third harmonics of the 28 ps Nd-YAG pulsed laser as a pumping beam for LiB3O5 optical parametrized generator using Z-scan method. Investigations performed by the Z-scan method were done during illumination by a Xe-F laser (lambda = 217 nm) as a photoinducing (pumping) beam. The pumping laser beam created a thin surface layer (about 80-90 nm) that was the source of the observed photoinduced TPA. The highest values of the TPA beta coefficients were achieved for polarization of the pumping light directed along the second-order crystallographic axis of the investigated crystals. The obtained values of the TPA coefficients were higher than those for the BiB3O6 crystals investigated earlier by us.

Journal Article↗

PubMed2006

Vibrational spectroscopy and ab initio studies of lithium bis(oxalato)borate (LiBOB) in different solvents.

The effect of lithium ion coordination with the bis(oxalato)borate (BOB-) [B(C2O4)2]- anion in DMSO, PEG, PPG, and d-PPG has been studied in detail by IR and Raman spectroscopy. Ab initio calculations were performed to allow a consistent analysis of the experimental data. The main features observed in the IR and Raman spectra correspond to the presence of "free", un-coordinated, BOB- anions. Only with use of d-PPG as solvent a small amount of Li+...BOB- ion pairs were detected. The Raman spectra and the calculations together indicate that Li+ coordinates bidentately with two end-oxygen atoms of the BOB- anion. The identification of ion pairs can be used to reveal limitations of LiBOB based electrolytes. The results for LiBOB are compared with literature on other Li salts.

Journal Article↗