973-17-1Relevant articles and documents
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.
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.
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)).
