Heterodinuclear Complexes Research Articles

Synthesis of heterodinuclear hydride complexes by oxidative addition of a transition-metal hydride to Pt(0) and Pd(0) complexes

Heterodinuclear hydridoplatinum and -palladium complexes, (dppe)HPt–MLn (MLn = MoCp(CO)3 (3a), WCp(CO)3 (3b)), (dppe)Pt(μ-H)(μ-CO)Mn(CO)4 (3c), (dppe)Pt(μ-H)(μ-CO)FeCp(CO) (3d), cis-L′2HPt–MLn (5aa: Lʹ = PPh3; MLn = MoCp(CO)3, 5ba: Lʹ = PPh3; MLn = WCp(CO)3, 5ab: Lʹ = PMePh2; MLn = MoCp(CO)3, 5ac: Lʹ = PMe2Ph; MLn = MoCp(CO)3), (dppe)Pd(μ-H)(μ-CO)MLn (MLn = MoCp(CO)2 (7a), WCp(CO)2 (7b)), (dppe)Pd(μ-H)(μ-CO)Mn(CO)4 (7c) are prepared by the oxidative addition of mononuclear transition-metal hydride complexes to zero-valent platinum or palladium complexes. The reactions of the heterodinuclear hydride complexes 3a, 3d and 7a with electron deficient alkenes and alkynes such as dimethyl fumarate or DMAD cause reductive elimination at the Pt or Pd center to give the Pt(alkene or alkyne)(dppe) and MHLn,, suggesting reversibility of this process. The DFT calculations suggest that these reactions are controlled by the thermodynamic stability and the electron rich alkene complex of Pt(0) (or Pd(0)) are preferable to prepare these heterodinuclear hydride complexes by the oxidative addition.

Chromium Complexes with N,N,N-Tridentate Quinolinyl Anilido-Imine Ligand: Synthesis, Characterization, and Catalysis in Ethylene Polymerization

The treatment of 2-(ArN═CH)C6H4-HNC9H6N ([NQNANIMe]H, Ar = 2,6-Me2C6H3; [NQNANIEt]H, Ar = 2,6-Et2C6H3; [NQNANIiPr]H, Ar = 2,6-iPr2C6H3) with nBuLi and CrCl3(THF)3 achieves the hetero-dinuclear complexes [NQNANIR]CrCl(μ-Cl)2Li(THF)2 (1a, R = Me; 1b, R = Et; 1c, R = iPr) or bisligated complex κ5-[NQNANIiPr]2CrCl (2c) depending on the reactant ratios used. Reactions of these ligands with nBuLi and CrCl2(THF)2 could achieve the square-pyramidal complexes [NQNANIR]CrCl(THF) (3b, R = Et; 3c, R = iPr). Complex 3c can be oxidized by alkyl chloride to dimeric complex {[NQNANIiPr]CrCl}2(μ-Cl)2 (4) through a single-electron-transfer mechanism. Similar reaction of 2-(C9H6N)N═CHC6H4-HNAr ([NQNINAMe]H, Ar = 2,6-Me2C6H3; [NQNINAEt]H, Ar = 2,6-Et2C6H3; [NQNINAiPr]H, Ar = 2,6-iPr2C6H3) with nBuLi and CrCl3(THF)3 furnishes [NQNINAR]CrCl(μ-Cl)2Li(THF)2 (5a, R = Me; 5b, R = Et; 5c, R = iPr) in high yields. However, a chromium complex with a butyl-substituted ligand, [NQBuNINAiPr]CrCl2 (6), is obtained when 2 equiv of nBuLi is used. The molecular structures of 1c, 2c, 3c, 4, 5c, and 6 are confirmed by X-ray crystallography. Upon activation with MAO, the Cr(III) complexes (1a–1c, 4, and 5a–5c) show moderate catalytic activities (50 to 218 kg of PE·mol(Cr)−1·h–1) in ethylene polymerization, whereas the Cr(II) complexes 2c, 3b, and 3c are inert under the same conditions.

Spin Adapted versus Broken Symmetry Approaches in the Description of Magnetic Coupling in Heterodinuclear Complexes

The performance of a series of wave function and density functional theory based methods in predicting the magnetic coupling constant of a family of heterodinuclear magnetic complexes has been studied. For the former, the accuracy is similar to other simple cases involving homodinuclear complexes, the main limitation being a sufficient inclusion of dynamical correlation effects. Nevertheless, these series of calculations provide an appropriate benchmark for density functional theory based methods. Here, the usual broken symmetry approach provides a convenient framework to predict the magnetic coupling constants but requires deriving the appropriate mapping. At variance with simple dinuclear complexes, spin projection based techniques cannot recover the corresponding (approximate) spin adapted solution. Present results also show that current implementation of spin flip techniques leads to unphysical results.

The First Heterotrinuclear Confacial Trioctahedron Ni II Ti IV Cr III : Rational Modular Assembly and Cooperative Effects

The heterodinuclear complex [(ioan)(NiTiIV)-Ti-II] with a facial O-3 donor set of Ti-IV-coordinated benzyl alcoholates serves as a metallo-ligand for a {(CrCl3)-Cl-III} fragment to yield the heterotrinuclear complex [(ioan)(NiTiCrCl3)-Ti-II-Cr-IV-Cl-III]. Comparisons of their molecular structures and electrochemical properties exhibit strong cooperative effects between the metal ions.

モノ（ホスフィン）パラジウム（0）錯体触媒による高活性Markovnikov型ヒドロメタル化反応：ヘテロ二核ヒドリドパラジウム中間体の合成と反応性

Syntheses of the heterodinuclear hydride complexes and their applications to catalytic hydrometallation reactions are described. Series of heterodinuclear palladium and platinum hydride complexes, L'2HPdMLn and L'2HPtMLn [L'=1/2 dppe, PMe3, PEt3, P(CH2Ph)3, PMe2Ph, PMePh2, PPh3, PCy3; MLn=MoCp(CO)3, WCp(CO)3, Mn(CO)5] are prepared by (i) the metathetical reaction of a mononuclear (halogeno)(hydrido)metal complex with an ate complex, (ii) the β-hydride elimination from the heterodinuclear ethyl complex, and (iii) the oxidative addition of a mononuclear hydride complex to a zerovalent metal complex. The reactions of L'2HPtMLn with electron-deficient alkenes lead to the reductive elimination to give the corresponding alkene complex of Pt(0) and MHLn. However, the similar treatment of L'2HPdMLn with electron-deficient alkenes gives the corresponding mononuclear alkyl complex MRLn. Mono(phosphine)palladium(0) complexes, Pd(diallyl ether)L' (L'=PPh3, PCy3, PMe3, PEt3) are found to be efficient active catalysts for the hydrometallation of electron-deficient alkenes of unreactive Mo, W, and Mn hydrides, MoHCp(CO)3, WHCp(CO)3, and MnH(CO)5. Scope and reaction mechanisms of the hydrometallation are described. This reaction involves a heterodinuclear hydridopalladium complex, L'HPdMLn as an active intermediate. An application of this catalysis to hydrosilylation of electron-deficient alkenes is also described.

Palladium(ii) mononuclear and palladium(ii)/ruthenium(ii) heterodinuclear complexes containing 2-quinolyl-substituted (pyridine-2-carbonyl)hydrazone.

A reaction of [PdCl2(cod)] (cod = 1,5-cyclooctadiene) and an E/Z mixture of quinoline-2-carbaldehyde (pyridine-2-carbonyl)hydrazone (HL) gave two kinds of Pd(II) mononuclear complexes, [PdCl(Z-L-κ(3)N,N',N'')] (1) and [PdCl2(E-HL'-κ(2)N,N')] (2), where L(-) is the deprotonated hydrazonate anion and HL' is the quinolinium-hydrazonate zwitterionic form of HL. Complex 2 is gradually converted to 1 in solution, and complex 1 is a good precursor to prepare a Pd(II)/Ru(II) heterodinuclear complex bridged by hydrazonate, trans(Cl,Cl)-[RuCl2(PPh3)2(μ-L)PdCl] (3).

Synthesis, structures and magnetism of heterodinuclear Ni–Ln complexes: field-induced single-molecule magnet behavior in the dysprosium analogue

Three isomorphous Ni–Ln heterodinuclear complexes were synthesized and structurally characterized. The Dy derivative exhibits field-induced single-molecule magnet behavior with an effective energy barrier of 16.9 K under a 1000 Oe dc field.

Structure-based description of a step-by-step synthesis of heterodinuclear ZnIILnIII complexes and their luminescence properties

The stepwise course of the synthesis of ZnIILnIII complexes of a new compartmental heptadentate open amide crown ether ligand has been investigated through the determination of the intermediate and final products occurring in the process. In the first step, the ligand L is reacted with Ln(NO3)3·5H2O to give the electroneutral complex [LnIIIL(NO3)3] with the lanthanide ion being linked to the N3O2 coordination site of the ligand which are fairly stable and could be isolated. Addition of Zn(NO3)3·6H2O to the [LnIIIL(NO3)3] complexes yield the desired heterodinuclear [ZnIILnIIIL(NO3)5(H2O)] complexes. In all [ZnIILnIIIL(NO3)5(H2O)] complexes, the ZnII ions invariably occupy the N3O2 site whereas the LnIII ions show preference for the carbonyl O site. Additionally, the solid-state photophysical properties of these complexes show that the sensitized EuIII- and TbIII-based luminescence can be enhanced after ZnII ion is incorporated.

Two new heterodinuclear Schiff base complexes: Synthesis, crystal structure and thermal studies

Two new heterodinuclear Schiff base complexes, [Hg(L)NiCl2(DMF)2] 1, and [Zn(L)NiCl2(DMF)2] 2, where H2L=N,N′-bis(salicylidene)-1,3-diaminopropane and DMF=dimethylformamide have been synthesized and characterized using elemental analysis, IR spectroscopy, thermal analysis and X-ray diffraction. Structural studies on 1 and 2 reveal the presence of a heterodinuclear [NiIIHgII] unit and [ZnIINiII] in which the central metal ions are connected to each other by two phenolate oxygen bridges. For complex 1 the Ni(II) ion adopts an elongated octahedral geometry (NiN2O4) while the Hg(II) ion assumes a distorted tetrahedral arrangement (HgO2Cl2) whereas for complex 2 the Zn(II) ion adopts an elongated octahedral geometry (ZnN2O4) while the Ni(II) ion assumes a distorted tetrahedral arrangement (NiO2Cl2). There are intermolecular CH···ClM interactions among the dinuclear complexes which are interconnected for 1 and 2. These intermolecular interactions result in the formation of a three dimensional structure for 1 and one dimensional zig-zag chains for 2.

Synthesis and characterization of CuII–LnIII (Ln = Ho, Tm, Yb, or Lu) complexes with N2O4-donor Schiff base ligand

The heterodinuclear complexes [CuLnL(NO3)2(H2O)3MeOH]NO3·MeOH (Ln = Ho (1), Tm (2), Yb (3), and Lu (4); L = N,N′-bis(5-bromo-3-methoxysalicylidene)propylene-1,3-diamine) have been synthesized and characterized by elemental analysis, FTIR, thermogravimetric (TG)/differential scanning calorimetry (DSC), TG-FTIR, single crystal X-ray diffraction studies, and magnetic measurements. The isostructural compounds crystallized in the monoclinic space group P21/n. The rare earth(III) cation is nine coordinate, whereas the coordination number for copper(II) is six. The complexes were stable at room temperature. The thermal decomposition products were mainly CH3OH, H2O, CH3Br, NOx (x = 1 or 2), CO2, and CO. The magnetic properties of 1–3 were dominated by the crystal field effect on the LnIII site, masking the magnetic interaction between the paramagnetic centers. The CuII–LuIII pair in 4 showed no significant interaction, which is in accord with the diamagnetic nature of the ground state for lutetium(III).

Systematic Heterodinuclear Complexes with MM′(μ-meppp) Centers That Tune the Properties of a Nesting Hydride (M = Ni, Pd, Pt; M′ = Rh, Ir; H2meppp = meso-1,3-Bis[(mercaptoethyl)phenylphosphino]propane)

Mononuclear complexes with a P2S2 ligand, [M(meppp)] (M = Ni (1a), Pd (1b), Pt (1c); H2meppp = meso-1,3-bis[(mercaptoethyl)phenylphosphino]propane), were treated with [M′Cp*Cl2]2 or [M′Cp*(NO3)2] (Cp* = η5-pentamethylcyclopentadienyl) to afford a series of bisthiolate-bridged MIIM′III heterodinuclear complexes, [M(μ-meppp)M′Cp*X]X′ (M = Ni, Pd, Pt; M′ = Rh, Ir; X = Cl, NO3; X′ = Cl, PF6, NO3). The nitrate complexes [M(μ-meppp)-M′Cp*(NO3)]NO3 (M′ = Rh ([4a–c]NO3), Ir ([5a–c]NO3); M = Ni (a), Pd (b), Pt (c)) further reacted with sodium formate in water or methanol to be transformed into bisthiolate- and hydride-bridged complexes, [M(μ-meppp)(μ-H)M′Cp*]NO3 (M′ = Rh ([6a–c]NO3), Ir ([8a–c]NO3); M = Ni (a), Pd (b), Pt (c)). Complexes [6a]NO3 (M = Ni, M′ = Rh) and [8a]NO3 (M = Ni, M′ = Ir) were characterized by X-ray analyses to reveal that a hydride is stabilized in a semibridging mode on the heterometal centers. In the PdIIRhIII ([6b]NO3) and PtIIRhIII ([6c]NO3) complexes, the hydrides were extremely unstable...

A Simple Decarbonylative Route to Heterodinuclear Alkylborylene Complexes

A new, photolytic route to heterodinuclear alkylborylene complexes is presented using the terminal manganese borylene complex [(η5-C5H5)(OC)2Mn(BtBu)]. Using this route, three new heterodinuclear alkylborylene complexes were prepared (Mn/Cr and Mn/Co), in addition to a known dimanganese alkylborylene complex usually prepared by salt elimination. The complexes have been characterized by NMR and IR spectroscopy as well as single-crystal X-ray crystallography. The overall picture gained from the spectroscopic and structural data is that the two metals in the Mn/Cr and Mn/Mn complexes appear to share the boron atom more evenly, while the cobalt fragment in the Mn/Co complex is more loosely bound to the boron atom.

A study on Zr-Ir multiple bonding active for C-H bond cleavage.

Zr-Ir hydrido complexes with ansa-(cyclopentadienyl)(amide) as the supporting ligand in the zirconium fragment, e.g., (L(1)ZrR)(Cp*Ir)(μ-H)3 [L(1) = Me2Si(η(5)-C5Me4)(N(t)Bu), R = Cl (5), Ph (7), Me (10), alkyl, and aryl] were designed, synthesized, and isolated as tractable early-late heterodinuclear complexes. Despite the presence of the three supporting hydride ligands, Zr-Ir distances in the crystal structures of 5, alkyl, and aryl complexes [2.74-2.76 Å] were slightly longer than the sum of the element radii of Zr and Ir [2.719 Å]. These hydrocarbyl complexes displayed the thermolytic C-H activation of a variety of aromatic compounds and several organometallic compounds. Also, the substrate scope and limitation in the Zr-Ir system were studied. The regiochemical outcomes during the C-H activation of pyridine derivatives and methoxyarenes suggested the in situ generation of a Lewis acidic active intermediate, i.e., (L(1)Zr)(Cp*IrH2) (III). The existence of III and relevant σ-complex intermediates {L(1)Zr(η(2)-R-H)}(Cp*IrH2) (IIR) (R = Me, Ph) in the ligand exchange was demonstrated by the direct isolation of a Et3PO-adduct of III (39b) from 7 and kinetic studies. The structure of the direct Zr-Ir bonds in IIPh, IIMe, III, and 39b were probed using computational studies. The unprecedented strong M-M' interactions in the early-late heterobimetallic (ELHB) complexes have been proposed herein.

A Heterodinuclear Complex OsIr Exhibiting Near-Infrared Dual Luminescence Lights Up the Nucleoli of Living Cells

The heterodinuclear metal complex OsIr has been designed and synthesized. Upon irradiation with visible light, OsIr exhibits dual luminescence (534 and 721 nm) due to the coexistence of the iridium and osmium activating centers. The cellular uptake of OsIr examined by laser scanning confocal microscopy revealed an apparent nucleolar staining. The iridium moiety interacts with proteins and RNA to trigger a significant luminescence enhancement, whereas the osmium moiety displays a near-infrared luminescence; a ratiometric luminescence response between the two moieties was observed upon protein addition.

Crystallographic evidence of metal scrambling in an N4O2-tetraiminodiphenolate macrocyclic complex

Heterodinuclear complexes [CuZn(tidf)(H2O)2(ClO4)2] and [CuMn(tidf)(H2O)2(ClO4)2] undergo intermolecular metal scrambling in water and water/acetonitrile solutions. X-ray diffraction, EPR and molecular magnetism unambiguously established the prominent species in solution and in the solid state. Spectroscopy properties in solution were in accordance with the presence of heterodinuclear complexes, while single-crystal determination revealed co-crystallization of homometallic CuIICuII and MIIMII (MZn or Mn) macrocyclic complexes.

Synthesis and structural characterization of a cyanide-bound heterodinuclear FeCo complex

Synthesis and structural characterization of a cyanide-bound heterodinuclear FeCo complex

Self-Assembly Synthesis, Structural Features, and Photophysical Properties of Dilanthanide Complexes Derived from a Novel Amide Type Ligand: Energy Transfer from Tb(III) to Eu(III) in a Heterodinuclear Derivative

A novel amide type ligand benzyl-N,N-bis[(2'-furfurylaminoformyl)phenoxyl)ethyl]-amine (L) has been designed and applied for the self-assembly generation of homodinuclear lanthanide coordination compounds [Ln2(μ2-L)2(NO3)6(EtOH)2] [Ln = Eu (1), Tb (2), and Gd (3)] and a heterodinuclear derivative [EuTb(μ2-L)2(NO3)6(EtOH)2] (4). All the complexes have been characterized by the X-ray single-crystal diffraction analyses. They are isostructural, crystallize in a monoclinic space group P21/c, and form [2 + 2] rectangular macrocycle structures. Compound 4 is the first example of a [2 + 2] rectangular macrocycle heterodinuclear EuTb complex assembled from an amide type ligand. In 4, the discrete 0D dimeric [EuTb(μ2-L)2(NO3)6(EtOH)2] units are extended, via the multiple N-H···O hydrogen bonds, into a 2D supramolecular network that has been topologically classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology. The triplet state ((3)ππ*) of L studied by the Gd(III) complex 3 demonstrated that the ligand beautifully populates Tb(III) emission (Φ = 52%), whereas the corresponding Eu(III) derivative 1 shows weak luminescence efficiency (Φ = 0.7%) because the triplet state of L has a poor match with (5)D1 energy level of Eu(III). Furthermore, the photoluminescent properties of heterodinuclear complex 4 have been compared with those of the analogous homodinuclear compounds. The quantum yield and lifetime measurements prove that energy transfer from Tb(III) to Eu(III) is being achieved, namely, that the Tb(III) center is also acting to sensitize the Eu(III) and enhancing Eu(III) emission in 4.

Synthesis of Heterodinuclear Hemisalen Complexes on a Hexaarylbenzene Scaffold and their Application for the Cross‐Pinacol Coupling Reaction

Intermolecular cross-pinacol coupling reaction between aliphatic and aromatic aldehydes by using heterodinuclear hemisalen complexes 1cis with vanadium(V) and titanium(IV) on a hexaarylbenzene scaffold is reported. Our ligand design is based on the individual activation of two aldehydes by vanadium and titanium, which are positioned with a suitable space on the rigid scaffold. Ligands such as 1cis were synthesized by Diels-Alder addition and decarbonylation reaction, followed by condensation of dialdehyde 3cis with various aminophenols. The influence of the substituents on the ligands on the pinacol coupling reaction was investigated. As a result, the reductive coupling reaction between aliphatic and aromatic aldehydes by using a catalytic amount of 1cis in the presence of Me3 SiCl and Zn provided the corresponding cross-coupled 1,2-diol in good yields with high cross-selectivity.

A heterodinuclear metal complex for direct imaging of rRNA in living cells.

A novel dual luminescence (523 nm and 615 nm) heterodinuclear RuIr complex for RNA detection was developed, which was successfully used to image rRNA in living cells.

Heterodinuclear complexes of 4,5-diazafluorene derivatives displaying η(5),κ(2)-[N,N] and η(5),κ(1)-N coordination modes.

The syntheses and structures for a series of heterodinuclear complexes of 4,5-diazafluorenyl (L(-)) and 3,6-dimesityl-4,5-diazafluorenyl (LMes(-)) ligands are reported herein. In all these heterodinuclear complexes, the Ru(II) centre is sandwiched between a pentamethylcyclopentadienyl (Cp*) ligand and the C5 ring of L(-) or LMes(-) in a double η(5) fashion, while the other metal (Fe(II), Co(II), Pt(II), or Cu(I)) is bound to the N-donors.