973-17-1Relevant academic research and scientific papers
Mercury(II) complexes of the carba- closo -dodecaboranyl ligands [ closo -1-CB11X11]2- (X = H, F, Cl, Br, I)
Himmelspach, Alexander,Sprenger, Jan A. P.,Warneke, Jonas,Zaehres, Manfred,Finze, Maik
, p. 1566 - 1577 (2012)
Salts of the mercury(II) complexes [Hg(closo-1-CB11X 11)2]2- (X = H (1), Cl (3), Br (4)) and [PhHg(closo-1-CB11X11)]- (X = H (6), Cl (8), Br (9), I (10)) were synthesized and characterized by multi-NMR spectroscopy, mass spectrometry, elemental analysis, and differential scanning calorimetry. Single crystals of Cs21?2Et2O, Cs23?MeCN, Cs24?4Me2CO, Cs9, and [Et4N]6?0. 5Me2CO were studied by X-ray diffraction, and the interpretation of the bond properties is supported by theoretical data. In contrast to the mercury atom of the previously published [Hg(closo-1-CB11F 11)2]2- (2), which coordinates either acetonitrile or water, the metal atom of the related dianionic complexes 1, 3, and 4 does not reveal any further coordination. According to results derived from DFT and ab initio calculations, this different behavior is reasoned in the case of 1 by a reduced Lewis acidity at mercury and in the case of 3 and 4 by the increased shielding of the central mercury atom as a result of the bulky halogenated carba-closo-dodecaboranyl ligands [closo-1-CB11X 11]2- (X = Cl, Br). The dianionic complex [Hg(closo-1-CB11I11)2]2- (5) with the bulkiest carba-closo-dodecaboranyl ligand was generated via collision-induced dissociation and characterized by (-)-ESI mass spectrometry. The fragmentation pathways of the anionic complexes [Hg(closo-1-CB 11X11)2]2- (X = H, F, Cl, Br, I (1-5)) and [PhHg(closo-1-CB11X11)]- (X = H, F, Cl, Br, I (6-10)) were studied by (-)-ESI mass spectrometry.
Transmetalation of Pentafluorophenylmercury Derivatives with Organylmagnesium Bromides
Bardin
, p. 1406 - 1408 (2019/08/21)
The reactions of pentafluorophenylmercury derivatives with organomagnesium compounds have been studied. The interaction of pentafluorophenylmercury chloride with RMgBr (R = Et, Ph) has afforded diphenyl- and diethylmercury or phenylmercury chloride, besides the expected product (C6F5HgR). The results have been explained by the transmetalation of C6F5HgR with the Grignard reagent, followed by the reaction of the resulting C6F5MgX (X = Br, C6F5) with pentafluorophenylmercury chloride. Transmetalation of (C6F5)2Hg with organylmagnesium bromides has led to the formation of C6F5MgX and R2Hg.
Synthesis of the molecular amalgam [{AuHg2(o-C6F4)3}{Hg3(o-C6F4)3}]-: A rare example of a heterometallic homoleptic metallacycle
Lasanta, Tania,López-De-Luzuriaga, José M.,Monge, Miguel,Olmos, M. Elena,Pascual, David
supporting information, p. 6334 - 6338 (2016/05/09)
The preparation of homoleptic heterometallic complexes still remains a challenge. Herein, we report the synthesis and characterization of [Au(PMe3)2][{AuHg2(o-C6F4)3}{Hg3(o-C6F4)3}] (1), a gold-mercury homoleptic metallacycle. The crystal structure of 1 displays two [Hg2M(o-C6F4)3] (M = AuI, HgII) units linked through a short Au?Hg contact of 3.097(2) ?, the strongest unsupported AuI?HgII interaction described to date. Theoretical calculations quantify the interaction between the trimetalic units as -199 kJ mol-1, a surprisingly strong value.
New syntheses and crystal structures of bis(fluorophenyl) mercury, Hg(Rf)2 (Rf = C6F5, 2,3,4,6-F4C6H, 2,3,5,6-F4C6H, 2,4,6-F3C6H2
Naumann, Dieter,Schulz, Frank
, p. 122 - 125 (2008/10/09)
Bis(fluorophenyl) mercury compounds, Hg(Rf)2 (Rf = C6F5, C6HF4, C6H 2F3, C6H3F2), are prepared in good yields by the reacti
Syntheses, characterizations, and crystal structures of β-diketiminato compounds of pentafluorophenyl group 12 derivatives, HC{[C(Me)N(C6H3-2,6-i-Pr2)]2}MC 6F5 (M = Zn, Cd)
Aboulkacem, Said,Tyrra, Wieland,Pantenburg, Ingo
, p. 1569 - 1574 (2008/10/08)
The reactions of H2C[C(Me)N(C6H 3-2,6-i-Pr2)]2 ((DPP)2NacNacH) and Zn(C6F5)2·2 EtCN or Cd(C 6F5)2·2 MeCN in a molar ratio of approximately 1:1 selectively gave the derivatives (DPP) 2NacNacMC6F5 (M = Zn, Cd) in excellent yields. No reaction was observed between (DPP)2NacNacH and Hg(C 6F5)2 under similar conditions. Reactions with Hg(C6F5)OCOMe yielded the products of dismutation, Hg(C6F5)2 and Hg(OCOMe)2. (DPP) 2NacNacZnC6F5 crystallises as a 1:1 adduct with THF with two independent molecules per unit cell (triclinic, P1 (no. 2)). The zinc atom is tetrahedrally surrounded by the chelating ligand, the pentafluorophenyl group and one THF molecule. A similar situation is found in the 1:1 adduct of (DPP)2NacNacCdC6F5 and DMF (monoclinic, P21/n (no. 14)), while in the donor-free compound (CDCl3 and H2O co-crystallize) the cadmium atom is nearly ideally trigonal planar co-ordinated (orthorhombic, Pbnm (no. 62)).
Syntheses and properties of tetrakis(pentafluorophenyl)tellurium, Te(C6F5)4, and related compounds - (See abstract)
Naumann, Dieter,Tyrra, Wieland,Herrmann, Rudolf,Pantenburg, Ingo,Wickleder, Mathias S.
, p. 833 - 842 (2008/10/08)
Te(C6F5)4 was prepared from the reactions of TeCl4 or Te(C6F5)2Cl2 with Grignard reagents or AgC6F5 in moderate to good yields. Substitution reactions with Me3SiX (X = Cl, Br, OSO2CF3), with equimolar amounts of Br2, with AgNO3 and with H[BF4] or BF3·OEt2 yielded the Te(C6F5)3X derivatives (X = Cl, Br, OSO2CF3, NO3, BF4). Oxidation reactions of Cd, Hg, and Pd0 complexes led to Te(C6F5)2 and the corresponding bis(pentafluorophenyl) derivatives M(C6F5)2 (M = Cd, Hg, Pd) and with InBr to In(C6F5)2Br. From very slow hydrolysis of Te(C6F5)4 the oxide Te(C6F5)2O was prepared. The thermal decomposition, the NMR and mass spectra of the partially new compounds are discussed. The crystal structures of Te(C6F5)3Br (monoclinic, P21/a, Z = 4), [Te(C6F5)3][OSO2CF3] (monoclinic, P21/n, Z = 16) and [Te(C6F5)2O]2 (triclinic, P1, Z = 2) were determined.
Silver compounds in synthetic chemistry. 1. A facile preparative route for pentafluorophenylsilver, AgC6F5 and its use as an oxidative pentafluorophenyl group transfer reagent in reactions with group 12 to 16 elements
Tyrra, Wieland,Wickleder, Mathias S.
, p. 1841 - 1847 (2008/10/08)
AgC6F5 is directly and quantitatively formed from room temperature reactions of AgF and Me3SiC6F5 in N-donor solvents, particularly EtCN. Solutions of AgC6F5 prepared by this method exhibit excellent oxidative properties in reactions with a variety of groups 12 to 16 elements giving the corresponding pentafluorophenyl element compounds in moderate to excellent yields. AgC6F5·EtCN crystallises with monoclinic symmetry (C2/c, Z = 8, a = 2301.4(5)pm, b = 1078.8(4)pm, c = 948.0(2)pm, β = 113.19(1)°) and exhibits chains of silver atoms with bridging C6F5 groups.
Bis(pentafluorophenyl)xenon, Xe(C6F5)2: A homoleptic diorganoxenon derivative
Maggiarosa, Nicola,Naumann, Dieter,Tyrra, Wieland
, p. 4588 - 4591 (2007/10/03)
A step forward in organo xenon chemistry: The fluoride-initiated reaction of Me3SiC6F5 and XeF2 leads, via the intermediate C6F5XeF, to an isolable [10-Xe-2] species with two xenon-carbon bonds (see scheme).
(Fluoroorgano)fluoroboranes and -fluoroborates I: Synthesis and spectroscopic characterization of potassium fluoroaryltrifluoroborates and fluoroaryldifluoroboranes
Frohn,Franke,Fritzen,Bardin
, p. 127 - 135 (2007/10/03)
A convenient preparation of K[ArBF3] (Ar=2-C6H4F, 3-C6H4F, 4-C6H4F, 2,6-C6H3F2, 3,5-C6H3F2, 2,4,6-C6H2F3, 3,4,5-C6H2F3, 2,3,4,5-C6HF4 and C6F5) is offered and the IR and multinuclear NMR spectra of these salts are reported. Treatment of the trifluoroborate salts with BF3 in chlorocarbon solvents provides an easy synthetic route to the corresponding aryldifluoroboranes ArBF2. The multinuclear NMR spectra of ArBF2 are presented. The electron substituent effect of the [-BF3]--group shows this substituent as one of the strongest σ-electron donors, while its π-electron influence is negligible (σI=-0.32, σR=-0.07).
SYNTHESIS AND PROPERTIES OF COVALENT TRI- AND TETRAVALENT VANADIUM
Razuvaev, G.A.,Latyaeva, V.N.,Vyshinskaya, L.I.,Drobotenko, V.V.
, p. 169 - 182 (2007/10/02)
Reactions of VCl3*3THF with RMgX (R = Ph, CH2SiMe3, C6F5) in various ratios have been studied.The stable compounds R3V*THF (R = CH2SiMe3, C6F5) were obtained.The chemical properties of R3V*THF, R4V*2L (R = CH2Ph, L = Et2O; R = C6F5, L = THF) and (Me3SiCH2)4V were investigated.Cleavage of the vanadium-carbonium ?-bond occurs in reactions with H2O, HCl and HgCl2.The insertion of carbon dioxide into the vanadium-carbon ?-bond was investigated.A scheme for the derivatives of tri- and tetravalent vanadium is proposed.Oxidative addition to (C6F5)3V*THF by Ph3CCl and VCl3*3THF was also studied.
