Dalton Transactions

doi: 10.1039/C3DT90108Dpmid: N/A

doi: 10.1039/c3dt90108dpmid: N/A

doi: 10.1039/c3dt90109bpmid: N/A

doi: 10.1039/C3DT90109Bpmid: N/A

doi: 10.1039/c3dt90110fpmid: N/A

doi: 10.1039/C3DT90110Fpmid: N/A

Iversen, Kalon J.; Wilson, David J. D.; Dutton, Jason L.

doi: 10.1039/c3dt51503fpmid: 23804120

A theoretical study focusing on the ring expansion that occurs in the reaction of N-heterocyclic carbenes with silanes has been carried out. A detailed reaction pathway was determined which indicates that formation of C–H bonds is the crucial factor in the transformation.

Alvarez, M. Angeles; Alvarez, Belén; García, M. Esther; García-Vivó, Daniel; Ruiz, Miguel A.

doi: 10.1039/c3dt51562apmid: 23807701

The sequential addition of H+ and H− ions to [Mo2Cp2(μ–κ2P,S:κ1P,η4-SPMes*)(CNtBu)(CO)2] (Mes* = 2,4,6-C6H2tBu3) completes a hydrocarbation or hydronitration of the uncoordinated CC bond of the Mes* ring, yielding new ligands with thiophosphinidene and aldimine or aminocarbene functions tethered to a η4-cyclohexadiene ring. The H− ion first attacks a Cp group to give a cyclopentadiene complex which evolves via a hydride intermediate.

Gao, Feng; Li, Yu-Yang; Liu, Cai-Ming; Li, Yi-Zhi; Zuo, Jing-Lin

doi: 10.1039/c3dt51051dpmid: 23818021

A new triple-decker dinuclear sandwich-type dysprosium complex based on both the phthalocyanine ligand and the tetradentate Schiff base ligand was synthesized, which is of interest for synthetic chemistry and also shows single-molecule magnetic behaviour.

Ryan, Patrick E.; Guénée, Laure; Piguet, Claude

doi: 10.1039/c3dt50941apmid: 23695775

The replacement of terminal benzimidazole–pyridine binding units in the neutral di-tridentate segmental ligand L1 with phenanthroline in L10 reduces the number of torsional degrees of freedom by two units. Reactions of these ligands with trivalent europium or lutetium cations yield structurally similar self-assembled dinuclear triple-stranded [Ln2(Lkkk)3]6+ complexes, thus demonstrating that the increased rigidity of the strand in L10 is compatible with its helical twist. With the larger lanthanum cations, the metallic coordination spheres are completed with two terminal axial triflate counter-anions to give [La2(L10)3(CF3SO3)2]4+. Thermodynamic investigations in acetonitrile confirm the minor constraints produced by the planar phenanthroline unit in L10 leading to comparable effective molarities EMEu,L1L1L1 ≈ EMEu,L10L10L10 = 10−3.9(4) M with mid-range EuIII cations. The striking minute effective molarities EMLn,LnLnLn-2H ≈ 10−6–10−9 M obtained upon the replacement of terminal phenanthrolines with structurally analogous fused hydroxyquinolines in L9 can be thus unambiguously assigned to solvation effects, a new tool for controlling complexity in metal-induced self-assembly processes.