Search results for "40"
showing 10 items of 17345 documents
Higher MLCT lifetime of carbene iron(ii) complexes by chelate ring expansion
2021
Combining strong σ-donating N-heterocyclic carbene ligands and π-accepting pyridine ligands with a high octahedricity in rigid iron(ii) complexes increases the 3MLCT lifetime from 0.15 ps in the prototypical [Fe(tpy)2]2+ complex to 9.2 ps in [Fe(dpmi)2]2+12+. The tripodal CNN ligand dpmi (di(pyridine-2-yl)(3-methylimidazol-2-yl)methane) forms six-membered chelate rings with the iron(ii) centre leading to close to 90° bite angles and enhanced iron-ligand orbital overlap.
Macrocyclic complexes based on [N⋯I⋯N]+ halogen bonds
2021
New 1–2 nm macrocyclic iodine(I) complexes prepared VIA a simple ligand exchange reaction manifest rigid 0.5–1 nm cavities that bind the hexafluorophosphate anion in the gas phase. The size of the cavities and the electrostatic interactions with the iodine(I) cations influence the anion binding properties of these macrocyclic complexes.
Highly Stable Neutral and Positively Charged Dicarbollide Sandwich Complexes
2005
Novel sandwich metallacarboranes commo-[3,3'-Ni(8-SMe2-1,2-C2B9H10)2] (1), commo-[3,3'-Co(8-SMe2-1,2-C2B9H10)2]+ (2+), commo-[3,3'-Ru(8-SMe2-1,2-C2B9H10)2] (4) and commo-[3,3'-Fe(8-SMe2-1,2-C2B9H10)2] (5) have been prepared by reaction of [10-SMe2-7,8-nido-C2B9H10]- with NiCl2 x 6 H2O, CoCl2, [RuCl2(dmso)4] and [FeCl2(dppe)], respectively. Reduction of 2+ with metallic Zn leads to the neutral and isolable complex commo-[3,3'-Co(8-SMe2-1,2-C2B9H10)2] (3). Theoretical calculations using the ZINDO/1 semiempirical method show three energy minima for complexes 1-3 and 5 that agree with the presence of three different rotamers in solution at low temperature, while four relative energy minima have…
A P-chirogenic β-aminophosphine synthesis by diastereoselective reaction of the α-metallated PAMP–borane complex with benzaldimine
2004
International audience; The diastereoselective synthesis of a P-chirogenic β-aminophosphine ligand with carbon–carbon bond formation of the ethano bridge in a 3:1 ratio via reaction of an α-metallated P-chirogenic phosphine borane with a benzaldimine is described. The diastereoselectivity is attributed to a transition state where the lithium cation chelates the phosphine borane carbanion and the nitrogen of the imine and the attack of the C@N occurs on the face opposite to the P–B bond, due to its interaction with the antibonding P–B bond. The major diastereoisomeric β-aminophosphine borane was then separated and decomplexed into the corresponding β-aminophosphine under neutral conditions a…
Palladium Catalyzed [3+2] Cycloaddition of Vinyl Aziridine and Indane-1,3-diones: Diastereo- and Enantioselective Access to Spiro-Pyrrolidines
2020
A mild and efficient palladium-catalyzed [3+2] cycloaddition of vinylaziridine and indane-1,3-diones has been realized. The resulting spiro-pyrrolidines were provided in excellent yields and, with the introduction of the leucine-derived phosphine ligand, moderate to good enantio- and diastereoselectivities.
Synthesis of 1,3-bis(trimethylcyclam) and 1,3-bis(trimethylcyclen) substituted benzenes
2009
Pd-catalyzed amination of 1,3-dibromobenzene with N,N',N''-trimethylcyclam and N,N',N''-trimethylcyclen provided corresponding 1,3-bis(tetraazamacrocyclic) derivatives of benzene in 25-32% yields. The dependence of the products yields on the phosphine ligand applied (BINAP, DavePHOS) as well as on the stoichiometry of starting compounds was established. Scope and limitations for the synthesis of N-phenyl and N-(3-bromophenyl) derivatives of trimethylcyclam and trimethylcyclen were demonstrated.
Design of bimetallic magnetic chains based on oxalate complexes: towards single chain magnets
2009
We describe the synthesis, structure and magnetic characterization of several oxalate-based bimetallic 1D systems. We will exemplify how by suitable choice of the molecular building blocks and strict control of their arrangement in the solid state, the magnetic properties of these low-dimensional materials can be tuned to finally obtain bimetallic oxalate chains behaving as single-chain magnets (SCM). First, we will focus on compounds [K(18-crown-6)][MII(bpy)Cr(ox)3] (1, 2; MII = Mn, Co; bpy = C10N2H8). The MnCr derivative behaves as a 1D ferromagnet down to 2 K, the lowest investigated temperature. The lack of magnetic ordering in this chain prompted us to prepare the more anisotropic MnCo…
The Cu(II) complex of a C-lipophilized 13aneN4 macrocycle with an additional protonable amino group as micellar anion receptor.
2009
Three 13aneN4 macrocyclic ligands have been prepared bearing a -CH(2)NHR side arm (R = H, n-C(5)H(11), n-C(10)H(21)) on a carbon atom. When Cu(2+) is complexed in the macrocyclic ring, the amino group of the side arm undergoes an acid-base protonation equilibrium but it is not able to coordinate apically the metal cation even when it is deprotonated. The Cu(2+) complex with the ligand bearing the longest appended aliphatic chain is fully confined inside Triton X-100 micelles, and its ability to bind and sequestrate a series of anions inside micelles has been studied at two different pH values, i.e. both with protonated and neutral side-arm amino group. The favourable role played by the prot…
PdII-mediated integration of isocyanides and azide ions might proceed via formal 1,3-dipolar cycloaddition between RNC ligands and uncomplexed azide
2016
Reaction between equimolar amounts of trans-[PdCl(PPh3)2(CNR)][BF4] (R = t-Bu 1, Xyl 2) and diisopropylammonium azide 3 gives the tetrazolate trans-[PdCl(PPh3)2(N4t-Bu)] (67%, 4) or trans-[PdCl(PPh3)2(N4Xyl)] (72%, 5) complexes. 4 and 5 were characterized by elemental analyses (C, H, N), HRESI+-MS, 1H and 13C{1H} NMR spectroscopies. In addition, the structure of 4 was elucidated by a single-crystal X-ray diffraction. DFT calculations showed that the mechanism for the formal cycloaddition (CA) of N3− to trans-[PdCl(PH3)2(CNMe)]+ is stepwise. The process is both kinetically and thermodynamically favorable and occurs via the formation of an acyclic NNNCN-intermediate. The second step of the fo…
Functionalized phosphonates as building units for multi-dimensional homo- and heterometallic 3d-4f inorganic-organic hybrid-materials.
2016
Using the multifunctional ligand H4L (2,2'-bipyridinyl-5,5'-diphosphonic acid), a new family of inorganic-organic hybrid-materials was prepared. The ligand shows a very high flexibility regarding the coordination mode, leading to a large structural diversity. The compounds 1a, 1b ([M(H2L)(H2O)4]·2.5H2O; M = Co(2+) (a), Ni(2+) (b)), 2 ([Gd2(H2H'L)2(H2H'2L)(H2O)6]Cl4·14H2O), 3a, 3b, 3c ([MCo(iii)(H2L)3(H2O)2]·6.5H2O; M = Gd(3+) (a), Dy(3+) (b) and Tb(3+) (c)), and 4 ([GdNi(ii)(H2L)3(H2O)3]NaCl·6H2O) were isolated and characterized with single crystal X-ray diffraction. Depending on the used metal ions and on the stoichiometry, either discrete entities (0D), extended 2D layers or 3D frameworks…