Synthesis, structure and hydrosilylation activity of neutral and cationic rare-earth metal silanolate complexes

Rare-earth metal alkyl tri(tert-butoxy)silanolate complexes [Ln{mu,eta2-OSi(O(t)Bu)3}(CH2SiMe3)2]2 (Ln = Y (1), Tb (2), Lu (3)) were prepared via protonolysis of the appropriate tris(alkyl) complex [Ln(CH2SiMe3)3(thf)2] with tri(tert-butoxy)silanol in pentane. Crystal structure analysis revealed a dinuclear structure for with square pyramidal geometry at the yttrium centre. The silanolate ligand coordinates in an eta2-bridging coordination mode giving a 4-rung truncated ladder and non-crystallographic inversion centre. Addition of two equiv. of 12-crown-4 to a pentane solution of 1 or 3 respectively gave [Ln{OSi(O(t)Bu)(3)}(CH2SiMe3)2(12-crown-4)].12-crown-4 (Ln = Y (4), Lu (5)). Crystal structure analysis of 5 showed a slightly distorted octahedral geometry at the lutetium centre. The silanolate ligand adopts an eta(1)-terminal coordination mode, whilst the crown ether unit coordinates in an unusual kappa3-fashion. Reaction of 1-3 with [NEt3H]+[BPh4]- in thf yielded the cationic derivatives [Ln{OSi(O(t)Bu)3}(CH2SiMe3)(thf)4]+[BPh4]- (Ln = Y (6), Tb (7) and Lu (8)); coordination of crown ether led to compounds of the form [Ln{OSi(O(t)Bu)3}(CH2SiMe3)(L)(thf)n]+[BPh4]- (Ln = Y, Lu, L = 12-crown-4, n = 1 (9,10); Ln = Y, Lu, L = 15-crown-5, n = 0 (11,12)). Reaction of 1 with [NMe2PhH]+[B(C6F5)4]-, [Al(CH2SiMe3)3] or BPh3 in thf gave the ion pairs [Y{OSi(O(t)Bu)3}(CH2SiMe3)(thf)4]+[A]- ([A]- = [B(C6F5)4]- (13), [Al(CH2SiMe3)4]- (14), [BPh3(CH2SiMe3)]- (15)), whilst two equiv. [NMe2PhH]+[BPh4]- with 1 in thf produced the dicationic ion triple [Y{OSi(O(t)Bu)3}(thf)6]2+[BPh4]-2 (16). Crystal structure analysis revealed that 16 is mononuclear with pentagonal bipyramidal geometry at the yttrium centre. The silanolate ligand coordinates in an eta(1)-terminal fashion. All diamagnetic compounds have been characterized by NMR spectroscopy. 1, 3, 4, 6 and 13 were tested as olefin hydrosilylation pre-catalysts with a variety of substrates; 1 was found to be highly active in 1-decene hydrosilylation.     

Synthesis and structures of the first cationic perfluoroaryllanthanoid(II) complexes

Tetraphenylborate salts of solvated pentafluorophenyllanthanoid(II) cations [Ln(C(6)F(5))(thf)(n)](+) (Ln=Eu, n=6 (1); Ln=Yb, n=5 (2)) were readily synthesized in high yield by reactions of ytterbium or europium with HgPh(C(6)F(5)) and Me(3)NHBPh(4) in THF. The structures of 1.THF and 2 confirmed the existence of well-separated ions and both 1 and 2 show notable thermal stability at room temperature. The cation in 2 was also observed in the remarkable mixed-valent complex [Yb(II)(C(6)F(5))(thf)(5)][Yb(III)(C(6)F(5))(2)[N(SiMe(3))(2)](2)] (3), fortuitously isolated in low yield from a reaction of ytterbium metal, HgPh(C(6)F(5)), and HN(SiMe(3))(2) in THF, and which additionally has an unusual bis(pentafluorophenyl)bis[bis(trimethylsilyl)amido)]ytterbate(III) anion. (171)Yb-(19)F coupling has been observed in the low-temperature (171)Yb NMR spectra of 2 and [Yb(C(6)F(5))(2)(thf)(4)].     

Anomalous structure-luminescence relationship in phosphorescent gold(I) isonitrile neutral complexes

A new compound that exhibits the shortest intermolecular Au...Au distance ever reported for neutral RNCAuX complexes is found to exhibit a counterintuitive higher-energy Au-centered phosphorescence than that in an analogous compound with a much longer Au...Au distance, presumably due to a different extent of excited-state distortion in dimers vs. extended chains.     

Synthesis and antitumor activity of DNA binding cationic porphyrin-platinum(II) complexes

A new series of DNA binding 5,10,15-tri(N-methyl-4-pyridiniumyl)porphyrin (TrisMPyP)-platinum(II) conjugates was synthesized, in which different spacer ligands were used for appropriate coordination to platinum(II) complexes. Compound 9b exhibited in vivo antitumor activity (T/C%, 294) superior to cisplatin (T/C%, 184) against the leukemia L1210 cell line.     

Synthesis and structure of phospholyl- and arsolylthulium(II) complexes

Reaction of thulium diiodide with substituted phospholide and arsolide salts respectively afforded stable bis(phospholyl)- and bis(arsolyl)thulium(II) complexes, that were characterised by multinuclear NMR and X-ray crystal structures, thus showing the beneficial effects of the steric and electronic properties of crowded phospholyl and arsolyl ligands for the stabilisation of divalent thulium.     

Synthesis of neutral and cationic monocyclopentadienyl alkyl niobium and tantalum complexes

Compound [NbCp′Me₄] (Cp′ = η⁵-C₅H₄SiMe₃, 1) reacted with several ROH compounds (R = tBu, SiiPr₃, 2,6-Me₂C₆H₃) to give the derivatives [NbCp′Me₃(OR)] (R = tBu 2a, SiiPr₃2b, 2,6-Me₂C₆H₃2c). The diaryloxo tantalum compound [TaCp^∗Me₂(OR)₂] (Cp^∗ = η⁵-C₅Me₅, R = 2,6-Me₂C₆H₃3) was obtained by reaction of [TaCp^∗Cl₂Me₂] with 2 equiv of LiOR (R = 2,6-Me₂C₆H₃). Abstraction of one methyl group from these neutral compounds 1-3 with the Lewis acids E(C₆F₅)₃ (E = B, Al) gave the ionic derivatives [NbCp′Me₂X][MeE(C₆F₅)₃] (X = Me 4-E. X = OR; R = SiiPr₃5b-E, 2,6-Me₂C₆H₃5c-E. E = B, Al) and [TaCp^∗Me(OR)₂][MeE(C₆F₅)₃] (R = 2,6-Me₂C₆H₃6-E; E = B, Al). Polymerization of MMA with the aryloxoniobium compound 2c and Al(C₆F₅)₃ gave syndiotactic PMMA in a low yield, whereas the tetramethylniobium compound 1 and the diaryloxotantalum derivative 3 were inactive.     

New neutral and cationic cyclopentadienylcobalt complexes

The treatment of the aquocation [Co(η³-2-MeC₃H₄)(η⁵-C₅H₅)(H₂O]⁺ with neutral and anionic ligands gives new cobalt complexes containing cations [Co(η³-2-MeC₃H₄)(η⁵-C₅H₅)L]ⁿ⁺, n = 0; L = CN, CH₃COO, CF₃COO and n = 1; L = P(p-MePh)₃, NCEt, NCPh, CNCy, dppm and [{Co(η³-2-MeC₃H₄)(η⁵-C₅H₅)}₂ (μ-L-L)]²⁺, L-L = bipy, dppm. The neutral cyano complex reacts with various electrophiles to give cationic isocyanide complexes containing the cation [Co(η³-2-MeC₃H₄)(η⁵-C₅H₅)(CNR)]⁺, which have been isolated in low yields. Chemical behaviour and structural implications of IR and ¹H and ¹³C NMR spectra are discussed.     

Acid Co(II) and Ni(II) trifluoroacetate complexes: Synthesis and crystal structure

Anhydrous and partially hydrated acid trinuclear trifluoroacetates of divalent transition metals of the composition [M₃(CF₃COO)₆(CF₃COOH)₆)](CF₃COOH) and [M₃(CF₃COO)₆(CF₃COOH)₂(H₂O)₄)](CF₃COOH)₂, respectively, where M = Co (I, III) Ni (II, IV), were synthesized and studied by X-ray diffraction. Complexes I and II were obtained by crystallization from solutions of M(CF₃COO)₂ · 4H₂O in trifluoroacetic anhydride; complexes III and IV were synthesized under the same conditions with the use of 99% trifluoroacetic acid as a solvent. Crystals I are triclinic: space group $P\bar 1$ , a = 13.199(6) Å, b = 14.649(6) Å, c = 15.818(6) Å, α = 90.04(4)°, β = 114.32(4)°, γ = 108.55(4)°, V = 2611.3(19) ų, Z = 2, R = 0.0480. Crystals II are trigonal: space group $R\bar 3$ , a = 13.307(2) Å, c = 53.13(1) Å, V = 8148(2) ų, Z = 6, R = 0.1112. Crystals III are triclinic: space group $P\bar 1$ , a = 9.001(8) Å, b = 10.379(9) Å, c = 12.119(9) Å, α = 83.67(5)°, β = 72.33(5)°, γ = 83.44(5)°, V = 1068.3(15) ų, Z = 1 Å, R = 0.1031. Crystals IV are triclinic: space group $P\bar 1$ , a = 9.121(18) Å, b = 10.379(2) Å, c = 12.109(2) Å, α = 84.59(3)°, β = 72.20(3)°, γ = 82.80(3)°, V = 1080.94(40) ų, Z = 1, R = 0.0334.     

Synthesis, structure and characterization of binuclear copper(Ⅱ) complexes

At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and pyridine N-oxide (triphenylphosphine oxide or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin) which affords the last products as binuclear copper(II) complexes, [Cu(C5H5NO)-(C6H5COO)2]2(1), [Cu(OPPh3)(C6H5COO)2]2(2) and [Cu(C6H5COO)(C26H2oN2)](3, C26H2oN2 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin). The structure of the complexes were characterized by elemental analyses, IR spectra, TG-DTA and magnetic property. Crystals(1) are triclinic, space group P1,a=0.92617(36),b=1.06973(17), c=1.08813(29) nm, a=59.60(2)°, β=74.83(3)°,γ=72.80(2)°, V=0.880 nm3, Dc=1.520 g/cm3, Z=1, R=0.044, Rw=0.048, Mr=805.78, 3477 reflections with I > 3σ(I). Each copper(Ⅱ) ion is coordinated by two bridging bidentate benzoate ligands and one pyridine N-oxide or triphenylphosphine oxide to form dimeric binuclear molecules. The structure of the compound(1) shows a clear centre of symmetry.     

Synthesis and X-ray crystal structure of oxamido-bridged heterobinuclear Ni(Ⅱ)-Cu(Ⅱ) complexes

The two complexes [Ni(oxen)Cu(L)2](ClO4)2.xH2O (L=2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen)) have been synthesized, where oxen is N,N'-bis(2-aminoethyl)oxamido di-anion. The crystal structure of [Ni(oxen)Cu(bpy)2](ClO4)2.CH3OH has been determined by X-ray diffraction method. The crystal is triclinic system, space group P1 with a=12.179(1),b=12.298(2), c=11.476(2) A, a=97.57(1), B=97.52(1), 7=80.29(2), V=1669.04(67) A3, Z=2, Dcalcd=1.667 g/cm3. The structure has been refined to final R of 0.076 and Rw of 0.080, respectively. The complexes have an extended oxamido-bridged structure and consist of Ni(Ⅱ) ion in a square planar environment and Cu(Ⅱ) ion in a distorted octahedral environment.     

Synthesis and crystal structure of thiolate-bridged dinuclear platinum(II) complexes

Russian Journal of General Chemistry - Reactions of 2,2′-bipyridine platinum(II) complexes with 2-aminoethanethiol or 2,2′-disulfanediyldi-(ethan-1-amine) afforded new complexes...     

Synthesis and catalytic properties of cationic palladium(II) and rhodium(I) complexes bearing diphosphinidinecyclobutene ligands

Cationic palladium(II) and rhodium(I) complexes bearing 1,2-diaryl-3,4-bis[(2,4,6-tri-t-butylphenyl)phosphinidene]cyclobutene ligands (DPCB–Y) were prepared and their structures and catalytic activity were examined (aryl = phenyl (DPCB), 4-methoxyphenyl (DPCB–OMe), 4-(trifluoromethyl)phenyl (DPCB–CF₃)). The palladium complexes [Pd(MeCN)₂(DPCB–Y)]X₂ (X = OTf, BF₄, BAr₄ (Ar = 3,5-bis(trifluoromethyl)phenyl)) were prepared by the reactions of DPCB–Y with [Pd(MeCN)₄]X₂, which were generated from Pd(OAc)₂ and HX in MeCN. On the other hand, the rhodium complexes [Rh(MeCN)₂(DPCB–Y)]OTf were prepared by the treatment of [Rh(μ-Cl)(cyclooctene)₂]₂ with DPCB–Y in CH₂Cl₂, followed by treatment with AgOTf in the presence of MeCN. The cationic complexes catalyzed conjugate addition of benzyl carbamate to α,β-unsaturated ketones.     

Synthesis and structure of Mn(II) and Zn(II) complexes containing 1,10-phenanthroline unit

The Mn(II) and Zn(II) complexes of N,N′-diisopropyl-1,10-phenanthroline-2,9-dimethanamine have been synthesised, and the structure of the two complexes have been studied by X-ray crystallography.     

Aggregation tendency and reactivity toward AgX of cationic half-sandwich ruthenium(II) complexes bearing neutral N,O-ligands

The aggregation tendency of complexes [Ru(eta6-cymene)(N,O)Cl]X [N,O = 2-benzoylpyridine (2-bzpy), 1, and 2-acetylpyridine (2-acpy), 2, X- = BPh4- or PF6-] has been studied by means of PGSE NMR experiments. It was found that complexes with PF6- as counterion are mainly present in CD2Cl2 as ion pairs at low concentration, as a mixture of ion triples and free anions at medium concentration and as ion quadruples at elevated concentration. 19F, 1H-HOESY NMR experiments revealed that in ion triples and ion quadruples two cationic Ru-units pair up. Consistently, in the solid-state structure of 1PF6, determined through X-ray single-crystal investigation, two cationic Ru-units are held together by an intermolecular pi-pi stacking interaction between the pyridyl rings. Complexes having BPh4- as counterion are only present in solution as even aggregates, namely ion pairs at low concentration and ion quadruples at elevated concentration. In such a case a counteranion bridges two cationic Ru-units as observed in the solid-state structure of 1BPh4. The reactivity of complexes 1-2 toward AgX salts has been investigated in different solvents. Bicationic [Ru(eta6-cymene)(N,O)(MeCN)]X2 (N,O = 2-bzpy, 3, and 2-acpy, 4) and [Ru(MeCN)4(N,O)]X2 (N,O = 2-bzpy, 5, and 2-acpy, 6) complexes were obtained by the reaction of 1 and 2 with AgX in the presence of three equivalents of acetonitrile or in acetonitrile, respectively. The reaction of 1 with AgPF6 in acetone afforded complex [Ru(eta6-cymene)(N,O,O)]PF6 (7, where N,O,O = 4-alcoxide-4-phenyl-4-(pyridin-2-yl)butan-2-one) from the C-C coupling of a deprotonated methyl group of the coordinated acetone and the C=O moiety of 2-bzpy ligand.     

Preparation of cationic chelate ylide complexes of palladium(II) and platinum(II)

Cationic palladium(II) and platinum(II) complexes with chelate ylides and neutral ligands of the type, [MCl (Y) (L)]⁺BPh₄^? (M  Pd or Pt; Y  bdep or bdmp*; L = 4-methylpyridine, 3,5-dimethylpyrazole, PPh₃, PCy₃, PMePh₂, P(OMe)₃, AsPh₃ or SbPh₃) and [M(bdep) (4-methylpyridine)₂] (BPh₄)₂ (M = Pd or Pt) were prepared and characterized by means of infrared and ¹H NMR spectra.     

Photochemistry of neutral isonitrile gold(I) complexes: modulation of photoreactivity by aurophilicity and pi-acceptance ability

This work demonstrates for the first time that aurophilicity and ligand pi-acceptance ability sensitize the photoreactivity of Au(I) complexes. Photolysis of LAu(I)Cl (L = RNC or CO) complexes leads to free L, Au(III), and Au(0) photoproducts. Solutions of (p-tosyl)CH(2)NCAuCl in dichloromethane undergo significant oligomerization leading to dimers and trimers with formation constants of 1.61 x 10(3) and 6.61 x 10(3) M(-1), respectively, representing the highest values reported to date for complexes that exhibit aurophilic association in solution. The photoproduct quantum yield (Phi) varies with the LAu(I)Cl concentration in solution. For (p-tosyl)CH(2)NCAuCl, metallic gold forms with Phi = 0.0065 and 0.032 in 4.0 x 10(-5) and 4.0 x 10(-3) M dichloromethane solutions, respectively. Meanwhile, irradiation of t-BuNCAuCl primarily produces t-BuNCAuCl(3) with Phi = 0.0045 and 0.013 for 5.0 x 10(-5) and 5.0 x 10(-3) M dichloromethane solutions, respectively. For Au(CO)Cl, metallic gold forms with Phi = 0.013 and 0.065 upon irradiation of 8.0 x 10(-5) and 8.0 x 10(-3) M dichloromethane solutions, respectively. Hence, *[LAuX](n) oligomeric species are more photoreactive than monomeric species. The results also demonstrate intuitive control of Phi via modulation of the pi-acceptance ability of L, as both follow CO > (p-tosyl)CH(2)NC > (alkyl)NC in LAuCl, a trend that is also commensurate with the relative long-term photosensitivity of the corresponding solids and solutions. A new method for preparing stable small gold nanoparticles is described based on the fundamental findings above. Thus, photolysis of different concentrations of LAuX in solutions containing a primary amine-terminated dendrimer leads to clear solutions exhibiting tunable visible plasmon absorptions of gold nanoparticles; these solutions maintain their colors and stability indefinitely. TEM measurements for representative samples prepared by photolysis of (p-tosyl)CH(2)NCAuCl solutions give rise to spherical nanoparticles as small as 5 nm.     

Synthesis, structure and catalytic activity of thioether-phosphane complexes of Pd(II) and Pt(II)

New thioether-phosphanes 2-RSC6H4CH2PPh2(RS-PPh2: R = Me, tBu, Ph) and the corresponding complexes [PdCl2(MeS-PPh2)], [PdCl2(tBuS-PPh2)], [PdCl2(PhS-PPh2)], [PdClMe(MeS-PPh2)] and [PtMe2(MeS-PPh2)] have been prepared, characterized and the X-ray crystal structures of all complexes determined. Whilst Pd(II) complexes of RS-PPh2 show low activity for CO/ethene copolymerisation, the complexes [PdCl2(RS-PPh2)] have been found to be very efficient for the Heck arylation of n-butylacrylate with bromobenzene under aerobic conditions.