heterodimetallic

The ability of the imine PyCH═N-CH2 Py (Py = 2-pyridyl, bpi) to behave as a heteroditopic ligand, which is suitable for creating two separate compartments to host metals in different oxidation states, has been developed by studying the reactions of the mixed-valence complexes [(cod)M-Ι (μ-bpi)MΙ (cod)] (M = Rh, Ir) with [M'(Cl)2 (PPh3 )2 ] (M' = Pd, Ni). The results depend on the molar ratio of the reagents used (1:1 or 1:2) to give the heterometallic complexes {d10 -M',d8 -M}-[(PPh3 )(Cl)M'0 (μ-bpi)MΙ (cod)] (Pd,Rh, 4 ; Pd,Ir, 5 ; Ni,Rh, 8 ; Ni,Ir, 9 ) and the two-electron mixed-valent compounds [(PPh3 )(Cl)M'0 (μ-bpi)M'ΙΙ (Cl)] (M' = Ni, 10 ; Pd, 11 ), respectively...

Herein, we present an unprecedented formation of a heterodinuclear complex [{(ppy)2 IrIII }(μ-phpy){RuII (tpy)}](ClO4 )2 {[ 1 ](ClO4 )2 } using terpyridyl/phenylpyridine as ancillary ligands and asymmetric phpy as a bridging ligand. The asymmetric binding mode (N∧ N-∩-N∧ N∧ C- ) of the phpy ligand in {[ 1 ](ClO4 )2 } is confirmed by 1 H, 13 C, 1 H-1 H correlated spectroscopy (COSY), high-resolution mass spectrum (HRMS), single-crystal X-ray crystallography techniques, and solution conductivity measurements...

Using ferrocene-based ligand systems, a series of heterobimetallic architectures of the general formula [Pd m L n ] x + were designed with the aim of installing an opening and closing mechanism that would allow the release and binding of guest molecules. Palladium complex formation was achieved through coordination to pyridyl groups, and using 2-, 3-, and 4-pyridyl derivatives provided access to defined PdL, PdL2 , and Pd2 L4 structures, respectively. The supramolecular complexes were characterized using nuclear magnetic resonance (NMR) and infrared spectroscopy, mass spectrometry, and elemental analysis, and for some examples density functional theory calculations and single-crystal X-ray diffraction analysis...

Novel monometallic (μ-LL')Ru, Ru(μ-LL'), homobimetallic Ru(μ-LL')Ru, and heterodimetallic Ru(μ-LL')Os and Os(μ-LL')Ru complexes based on two asymmetrical ligands LL' (where LL' = L1 L1' , L2 L2' ) have been synthesized and characterized. Spectroscopic analysis indicates that all complexes exhibit intense spin-allowed ligand-centered (LC) transitions at 288 nm and Ru-based moderate spin-allowed MLCT absorption between 440-450 nm. The Ru(μ-LL')Os and Os(μ-LL')Ru dinuclear complexes show Os-based unit absorption in the range of 565-583 nm...

The reaction of a terminal Mo(II) nitride with a U(III) complex yields a heterodimetallic U-Mo nitride which is the first example of a transition metal-capped uranium nitride. The nitride is triply bonded to U(V) and singly bonded to Mo(0) and supports a U-Mo interaction. This compound shows reactivity toward CO oxidation.

Multimetallic complexes have been shown in several examples to possess greater anticancer activity than their monometallic counterparts. The increased activity has been attributed to altered modes of action. We herein report the synthesis of a series of heterodimetallic compounds based on a ditopic ligand featuring 2-pyridylimine chelating motifs and organometallic half-sandwich moieties. The complexes were characterized by a combination of 1 H NMR spectroscopy, electrospray ionization mass spectrometry, elemental analysis and single crystal X-ray diffraction...

Heterotrimetallic complexes (NiAuAg, PdAuAg, PtAuAg, and NiAuCu) containing a tritopic N -heterocyclic carbene (NHC) have been synthesized for the first time through the deprotonation and metalation of heterodimetallic complexes and were structurally characterized by single-crystal X-ray diffraction. The carbene character of the donor groups in the tritopic NHC complexes was established on the basis of structural and NMR analyses.

Open-ended, singly metalated dithiolene complexes with 1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz) are prepared either by ligand transfer to [Cl2 M(tpbz)] from (R2 C2 S2 )SnR'2 (R = CN, R' = Me; R = Me, R' = n Bu) or by a direct reaction between tpbz and [M(S2 C2 R2 )2 ] (M = Ni, Pd, Pt; R = Ph, p -anisyl) in a 1:1 ratio. The formation of dimetallic [(R2 C2 S2 )M(tpbz)M(S2 C2 R2 )] attends these syntheses in modest amounts, but the open-ended compounds are readily separated by silica chromatography. As affirmed by X-ray crystallographic characterization of numerous members of the set, the [(R2 C2 S2 )M(tpbz)] compounds show dithiolene ligands in their fully reduced ene-1,2-dithiolate form conjoined with divalent Group 10 ions...

The ligand H 3 L (6-(3-oxo-3-(2-hydroxyphenyl)propionyl)-pyridine-2-carboxylic acid), which exhibits two different coordination pockets, has been exploited to engender and study energy transfer (ET) in two dinuclear [Ln(III)Ln(III)'] analogues of interest, [EuYb] and [NdYb]. Their structural and physical properties have been compared with the also newly synthesised analogues featuring no possible ET ([EuLu], [NdLu] and [GdYb], respectively) and with the corresponding homometallic [EuEu] and [NdNd] analogues, previously reported...

The heterodimetallic [CuFe] compounds [CuII 4 (terpy)4 Cl5 ][FeIII (C2 O4 )3 ]·10H2 O ( 1 ;terpy = 2,2':6',2''-terpyridine), [CuII 2 (H2 O)2 (terpy)2 (C2 O4 )][CuII FeIII (CH3 OH)(terpy)(C2 O4 )3 ]2 ( 2 ), and {[Cu2 II FeIII (H2 O)(terpy)2 (C2 O4 )7/2 ]·6H2 O} n ( 3 ) were obtained using building block approach, from reaction of aqueous solution of [Fe(C2 O4 )3 ]3- and a methanol solution containing Cu2+ ions and terpy by the layering technique. Interestingly, by changing only the anion of the starting salt of copper(II), Cu(NO3 )2 ·3H2 O instead of CuCl2 ·2H2 O, an unexpected change in the type of bridge, oxalate ( 2 and 3 ) versus chloride ( 1 ), was achieved, thus affecting the overall structural architecture...

One-dimensional (1D) oxalate-bridged homometallic {[Mn(bpy)(C2 O4 )]·1.5H2 O} n ( 1 ) (bpy = 2,2'-bipyridine) and heterodimetallic {[CrCu3 (bpy)3 (CH3 OH)(H2 O)(C2 O4 )4 ][Cu(bpy)Cr(C2 O4 )3 ]·CH2 Cl2 ·CH3 OH·H2 O} n ( 2 ) coordination polymers, as well as the three-dimensional (3D) heterotrimetallic {[CaCr2 Cu2 (phen)4 (C2 O4 )6 ]·4CH3 CN·2H2 O} n ( 3 ) (1,10-phenanthroline) network, have been synthesized by a building block approach using a layering technique, and characterized by single-crystal X-ray diffraction, infrared (IR) and impedance spectroscopies and magnetization measurements...

The synthesis and characterization of the novel ferrocenyl sulfonyl hydrazide [Fe(η5-C5H5){(η5-C5H4)-S(O)2-NH-NH2}] (2) is reported. Additional studies on its reactivity using acetone or the ferrocenyl-, cyrhetrenyl- or cymantrenyl-aldehydes have allowed us to isolate and characterize [Fe(η5-C5H5){(η5-C5H4)-S(O)2-NH-N[double bond, length as m-dash]CMe2}] (3), the bis(ferrocenyl) derivative [Fe(η5-C5H5){[(η5-C5H4)-S(O)2-NH-N[double bond, length as m-dash]CH-(η5-C5H4)]Fe(η5-C5H5)}] (4) and the heterodimetallic compounds [Fe(η5-C5H5){[(η5-C5H4)-S(O)2-NH-N[double bond, length as m-dash]CH-(η5-C5H4)]M(CO)3}] with M = Re (5a) or Mn (5b)...

For C-H alkenylation of aryl-substituted diarylisoxazoles, one mode is N-directed C-H alkenylation and the other is C-H alkenylation in the isoxazole ring. In this study, selective C-H alkenylations of 3,5-diarylisoxazoles have been investigated theoretically with the aid of density functional theory (DFT) calculations. With Cp*RhIII as the catalyst, the N-directed C-H alkenylation is preferred as a result of the stronger interaction energy caused by the nitrogen-directing effect. With Pd(OAc)2 as the catalyst and Ag2 CO3 as the cocatalyst, their combination switches the regioselectivity to the C-H alkenylation in the isoxazole ring...

Potentiometric speciation studies, mass spectrometry, and DFT calculations helped to predict the various structural possibilities of the dinuclear trivalent lanthanide ion (LnIII , Ln=La, Eu, Tb, Yb, Y) complexes of a novel macrocyclic ligand, m-ODO2A-dimer (H4 L), to correlate with their luminescence properties and the promoted BNPP and HPNP phosphodiester bond hydrolysis reaction rates. The stability constants of the dinuclear Ln2 (m-ODO2A-dimer) complexes and various hydrolytic species confirmed by mass spectrometry were determined...

The kinetic lability of hexadentate gallium-based tripods is sufficient to ensure thermodynamic self-assembly of luminescent heterodimetallic [GaLn(L3)3 ](6+) helicates on the hour time scale, where Ln is a trivalent 4f-block cation. The inertness is, however, large enough for preserving the triple-helical structure when [GaLn(L3)3 ](6+) is exposed to lanthanide exchange. The connection of a second gallium-based tripod further slows down the exchange processes to such an extent that spectroscopically active [CrErCr(L4)3 ](9+) can be diluted into closed-shell [GaYGa(L4)3 ](9+) matrices without metal scrambling...

To force metal ions in heterometallic coinage metal complexes into preset compartments, we have synthesized a ligand with two N-heterocyclic carbenes (NHCs) separated by a methylene bridge and two bipyridine moieties tethered to each NHC moiety. By using this ligand, tetranuclear heterodimetallic gold/copper and gold/silver complexes were obtained. These complexes show an unprecedented V-shape or linear MAu2 M (M = Cu, Ag) configuration in the solid state. The photophysical properties of the new compounds are significantly affected by the complexed metal ions...

The solid-state and solution configurations of the heterodimetallic complexes (Hpy)[LaEr(HL)3 (NO3 )(py)(H2 O)] (1), (Hpy)[CeEr(HL)3 (NO3 )(py)(H2 O)] (2), (Hpy)[CeGd(HL)3 (NO3 )(py)(H2 O)] (3), (Hpy)[PrSm(HL)3 (NO3 )(py)(H2 O)] (4), and (Hpy)2 [LaYb(HL)3 (NO3 )(H2 O)](NO3 ) (5), in which H3 L is 6-(3-oxo-3-(2-hydroxyphenyl)propionyl)pyridine-2-carboxylic acid and py is pyridine, were analyzed experimentally and by using DFT calculations. Complexes 3, 4, and 5 are described here for the first time, and were analyzed by using single-crystal X-ray diffraction and mass spectrometry...

Trinuclear versus dinuclear heterodimetallic UV O2 + Co2+ complexes were selectively assembled via a cation-cation interaction by tuning the ligand. The trimeric complex 2, with a linear [Co-O[double bond, length as m-dash]U[double bond, length as m-dash]O-Co] core, exhibits magnetic exchange and slow relaxation with a reversal barrier of 30.5 ± 0.9 K providing the first example of a U-Co exchange-coupled SMM.

The first K/Cd heterodimetallic complex {[Cd1.5 (TTPE)1.5 Cl3 K(H2 O)3 ]·3H2 O}n (1b) based on triazole has been generated from {[Cd(TTPE)(HCOO)](NO3 )·3DMAC·H2 O}n (1) during the ion- and solvent-exchange experiment in an irreversible SC-SC transformation. Based on its luminescence properties, we have, for the first time, demonstrated that 1b is a heterodimetallic sensor for detection of high-explosives and cyano molecules.

Heterodimetallic Ru-Fe complexes [(tppz)(PPh3)2RuL](ClO4) (L = C[triple bond, length as m-dash]CFc, [](ClO4); C[triple bond, length as m-dash]C-C6H4-C[triple bond, length as m-dash]CFc), [](ClO4); C[triple bond, length as m-dash]C-C6H4-C6H4-C[triple bond, length as m-dash]CFc, [](ClO4)) were synthesized by the reactions of [(tppz)(PPh3)2RuCl](ClO4) (tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine) with ferrocence-acetylide ligands and characterized by ESI-MS, and (1)H and (31)P NMR spectroscopies. The structure of [](PF6) was determined by X-ray crystallography...