Soluble Heterometallic Coordination Polymers Based on a Bis-terpyridine-Functionalized Dioxocyclam Ligand
Soluble homo- and heterometallic coordination polymers containing transition metal cations (Cu(2+), Fe(2+), Co(2+), and Ni(2+) ions) were prepared in a two-step procedure using a polytopic bis(terpyridine)dioxocyclam ligand 1H(2) (dioxocyclam = 1,4,8,11-tetraazacyclotetradecane-5,7-dione). These supramolecular systems incorporate two different metal complexes, the metal cations being located both between two terpyridine units and in the macrocyclic framework. The characterization of these soluble architectures was investigated by cyclic voltammetry, mass spectrometry, viscosimetry, and UV-vis absorption and electron paramagnetic resonance (EPR) spectroscopies. Our results clearly indicate t…
On the Road to MM′X Polymers: Redox Properties of Heterometallic Ni···Pt Paddlewheel Complexes
On the quest of heterometallic mixed-valence MM'X chains, we have prepared two stable discrete bimetallic compounds: the reduced (PPN)[ClNi(μ-OSCPh)4Pt] (PPN = bis(triphenylphosphine)iminium; OSCPh = benzothiocarboxylato) and the oxidized [(H2O)Ni(μ-OSCPh)4PtCl] species. The role of the aqua and chlorido axial ligands is crucial to facilitate oxidation of the {Ni(μ-OSCPh)4Pt} core. Experimental and theoretical analyses indicate that a NiPt-Cl/Cl-NiPt isomerization process occurs in the oxidized species. The electronic structure of the reduced system shows two unpaired electrons, one located in a d(x(2)-y(2)) orbital of the Ni(II) ion and a second in the antibonding d(z(2)-dz(2)) combination…
A tetranuclear organorhenium(i) complex of the 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane radical anion, TCNQF4˙−
The radical complex {(mu(4)-TCNQF4)[Re(CO)(3)(bpy)](4)}(PF(6))(3), as prepared and isolated from the reaction between TCNQF4 and [Re(CO)(3)(bpy)(MeOH)](PF(6)), was studied electrochemically and by IR vibrational spectroscopy, UV-Vis-NIR absorption spectroscopy, and by EPR at 9.5, 190 and 285 GHz. The isotropic g factor of 2.0058, the detectable g anisotropy, and the (185,187)Re EPR hyperfine coupling of 0.95 mT for four equivalent metal nuclei support predominant, but not exclusive, spin localisation at the bridging ligand. Nitrile and metal carbonyl stretching frequencies as well as the typically structured near infrared absorption band lend further support to (TCNQF4 (-))(Re(I))(4) as the…
Heterotetranuclear Complexes of Reduced and Non-reduced Bridging 1,2,4,5-Tetrazine Ligands with 1,1′-Bis(diphenylphosphanyl)-ferrocene-copper(I)
The complexes {(μ-bptz)[Cu(dppf)]2}(BF4)2 [(1)(BF4)2] [bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, dppf = 1,1′-bis(diphenylphosphanyl)ferrocene] and {(μ-bpztz)[Cu(dppf)]2}(PF6)2 [(2)(PF6)2] [bpztz = 3,6-bis(2-pyrazinyl)-1,2,4,5-tetrazine] contain two redox-active heterodinuclear FeIICuI moieties, bridged by a redox-active ligand. A crystal structure determination of (1)(BF4)2·2CH2Cl2 confirms the non-reduced aromatic nature of the bridge, in contrast to previous results on dicopper(I) complexes of bptz. Facile one-electron reduction produces the radical complexes {(μ-bptz)[Cu(dppf)]2}+ (1+) and {(μ-bpztz)[Cu(dppf)]2}+ (2+), which could be isolated [as (1)(BF4)] and studied by variable freq…
CCDC 1013364: Experimental Crystal Structure Determination
Related Article: Marcello Gennari, Gonzalo Givaja, Oscar Castillo, Laura Hermosilla, Carlos J. Gómez-García, Carole Duboc, Agustí Lledós, Ruben Mas-Ballesté, and Felix Zamora|2014|Inorg.Chem.|53|10553|doi:10.1021/ic501659x
CCDC 1013365: Experimental Crystal Structure Determination
Related Article: Marcello Gennari, Gonzalo Givaja, Oscar Castillo, Laura Hermosilla, Carlos J. Gómez-García, Carole Duboc, Agustí Lledós, Ruben Mas-Ballesté, and Felix Zamora|2014|Inorg.Chem.|53|10553|doi:10.1021/ic501659x