Dinuclear copper complexes with cyanamide derivatives as bridging ligands

Three mixed-valence copper complexes [{Cu(phen)₂}₂(μ-L)](PF₆)₂ (where phen = 1,10-phenanthroline, L = 1,4-dicyanamidobenzene (dicyd)), 1,4-dicyanamido-2,5-dimethylbenzene (Me₂dicyd) and 1,4-dicyanamido-2,5-dichlorobenzene (Cl₂dicyd), and one dinuclear Cu(II) complex [{Cu(phen)₂}₂(μ-apc)](PF₆)₃ (where apc = monoanion of 4-azo(phenylcyanamido)benzene) have been prepared and characterized by elemental analysis, IR and electronic absorption spectroscopies and cyclic voltammetry. [{Cu(phen)₂}₂(μ-apc)](PF₆)₃ · 2CH₃COCH₃ crystallized in the triclinic system and both five-coordinate Cu(II) ions in the dinuclear unit are linked through a bridging 4-azo(phenylcyanamido)benzene (apc) ligand. The cyanamide group (NCN) of the bridging ligand is coordinated to Cu(II) ions through the cyano-nitrogen and amido-nitrogen. The bond length between Cu(1) and cyano-nitrogen is slightly larger than that formed by Cu(2) and amido-nitrogen. The angular structural index parameters, τ, for Cu(1) and Cu(2) are 0.9 and 0.5, respectively. The copper(II) atoms display a different geometry with a N₅ chromophore group. The intra Cu?Cu separation is 5.156(1) Å. All of the dicyd dinuclear copper complexes show radical anion absorption.     

Self-assembly organometallic squares with terpyridyl metal complexes as bridging ligands

A series of novel heterometallic square complexes with the general molecular formulas [fac-Br(CO)(3)Re[mu-(pyterpy)(2)M]](4)(PF(6))(8) and [(dppf)Pd[mu-(pyterpy)(2)Ru]](4)(PF(6))(8)(OTf(8) (4), where M = Fe (1), Ru (2), or Os (3), pyterpy is 4'-(4' "-pyridyl)-2,2':6',2' '-terpyridine, dppf = 1,1'-bis(diphenylphosphino)ferrocene and OTf is trifluoromethanesulfonate, were prepared by self-assembly between BrRe(CO)(5) or (dppf)Pd(H(2)O)(2)(OTf)(2) and (pyterpy)(2)M(PF(6))(2). The obtained NMR spectra, IR spectra, electrospray ionization mass spectra, and elemental analyses are all consistent with the proposed square structures incorporating terpyridyl metal complexes as bridging ligands. Multiple redox processes were observed in all square complexes. All four complexes display strong visible absorptions in the region 400-600 nm, which are assigned as metal (Fe, Ru, or Os)-to-ligand (pyterpy) charge transfer (MLCT) bands. Square 3 exhibits an additional weak band at 676 nm, which is assigned to an Os-based (3)MLCT band. For each complex, the bands centered between 279 and 377 nm are assigned as pyterpy-based pi-pi bands and the Re-based MLCT band. Square 3 is luminescent in room-temperature solution, while squares 1, 2, and 4 do not have any detectable luminescence under identical experimental conditions.     

Dimolybdenum cyclopentadienyl complexes with bridging chalcogenophosphinidene ligands

The reactions of the phosphinidene-bridged complex [Mo(2)Cp(2)(μ-PH)(η(6)-HMes*)(CO)(2)] (1), the arylphosphinidene complexes [Mo(2)Cp(2)(μ-κ(1):κ(1),η(6)-PMes*)(CO)(2)] (2), [Mo(2)Cp(2)(μ-κ(1):κ(1),η(4)-PMes*)(CO)(3)] (3), [Mo(2)Cp(2)(μ-κ(1):κ(1),η(4)-PMes*)(CO)(2)(CN(t)Bu)] (4), and the cyclopentadienylidene-phosphinidene complex [Mo(2)Cp(μ-κ(1):κ(1),η(5)-PC(5)H(4))(η(6)-HMes*)(CO)(2)] (5) toward different sources of chalcogen atoms were investigated (Mes* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5)). The bare elements were appropriate sources in all cases except for oxygen, in which case dimethyldioxirane gave the best results. Complex 1 reacted with the mentioned chalcogen sources at low temperature, to give the corresponding chalcogenophosphinidene derivatives [Mo(2)Cp(2){μ-κ(2)(P,Z):κ(1)(P)-ZPH}(η(6)-HMes*)(CO)(2)] (Z = O, S, Se, Te; P-Se = 2.199(2) ?). The arylphosphinidene complex 2 was the least reactive substrate and gave only chalcogenophosphinidene derivatives [Mo(2)Cp(2)(μ-κ(2)(P,Z):κ(1)(P),η(6)-ZPMes*)(CO)(2)] for Z = O and S (P-O = 1.565(2) ?), along with small amounts of the dithiophosphorane complex [Mo(2)Cp(2)(μ-κ(2)(P,S):κ(1)(S'),η(6)-S(2)PMes*)(CO)(2)], in the reaction with sulfur. The η(4)-complexes 3 and 4 reacted with sulfur and gray selenium to give the corresponding derivatives [Mo(2)Cp(2)(μ-κ(2)(P,Z):κ(1)(P),η(4)-ZPMes*)(CO)(2)L] (L = CO, CN(t)Bu), obtained respectively as syn (Z = Se; P-Se = 2.190(1) ? for L = CO) or a mixture of syn and anti isomers (Z = S; P-S = 2.034(1)-2.043(1) ?), with these diastereoisomers differing in the relative positioning of the chalcogen atom and the terminal ligand at the metallocene fragment, relative to the Mo(2)P plane. The cyclopentadienylidene compound 5 reacted with all chalcogens, and gave with good yields the chalcogenophosphinidene derivatives [Mo(2)Cp(μ-κ(2)(P,Z):κ(1)(P),η(5)-ZPC(5)H(4))(η(6)-HMes*)(CO)(2)] (Z = S, Se, Te), these displaying in solution equilibrium mixtures of the corresponding cis and trans isomers differing in the relative positioning of the cyclopentadienylic rings with respect to the MoPZ plane in each case. The sulfur derivative reacted with excess sulfur to give the dithiophosphorane complex [Mo(2)Cp(μ-κ(2)(P,S):κ(1)(S'),η(5)-S(2)PC(5)H(4))(η(6)-HMes*)(CO)(2)] (P-S = 2.023(4) and 2.027(4) ?). The structural and spectroscopic data for all chalcogenophosphinidene complexes suggested the presence of a significant π(P-Z) bonding interaction within the corresponding MoPZ rings, also supported by Density Functional Theory calculations on the thiophosphinidene complex syn-[Mo(2)Cp(2)(μ-κ(2)(P,S):κ(1)(P),η(4)-SPMes*)(CO)(3)].     

Pnictides as symmetrically bridging ligands in novel neutral complexes

The reaction of [LWCl] (3) [L = N(CH2CH2NiPr)3] with LiE(SiMe3)2 (E = P, As, Sb) yields the novel, neutral pnictido-bridged complexes [LW = E = WL] (5-7). By following the reaction, which starts from the LiP-(SiMe3)2 derivative, by 31P NMR spectroscopy, the formation of an intermediate with a terminal pnictido ligand can be ruled out. The paramagnetic complexes 5-7 are comprehensively spectroscopically characterised. The X-ray structure analysis of the heterocumulenes 5-7 reveals a linear structure in which the two W-"tren" units bind to the central pnictido atom in a staggered conformation ["tren" = tren-based ligand; tren = tris(2-aminoethyl)-amine. When N2 is used as the inert gas in the synthesis of the starting material [N(CH2CH2NNp)3WCl] [Np = CH2C-(CH3)3], the complex [[N(CH2CH2NNp)3]W2(mu, eta 1: eta 1-N2)] (4) is formed as a side product. Complex 4 possesses a hydrazido(4-) (N2(4-)) ligand connected by two tungsten-"tren" moieties.     

Rhodium cluster complexes containing bridging phenylgermanium ligands

The reaction of Rh(4)(CO)(12) with Ph(3)GeH at 97 degrees C has yielded the first rhodium cluster complexes containing bridging germylene and germylyne ligands: Rh(8)(CO)(12)(mu(4)-GePh)(6), 9, and Rh(3)(CO)(5)(GePh(3))(mu-GePh(2))(3)(mu(3)-GePh)(mu-H), 10. When the reaction is performed under hydrogen, the yield of 9 is increased to 42% and no 10 is formed. Compound 9 contains a cluster of eight rhodium atoms arranged in the form of a distorted cube. There are six mu(4)-GePh groups bridging each face of this distorted cube. Four of the rhodium atoms have two terminal carbonyl ligands, while the remaining four rhodium atoms have only one carbonyl ligand. Compound 10 contains a triangular cluster of three rhodium atoms with one terminal GePh(3) ligand, three bridging GePh(2) ligands, and one triply bridging GePh ligand. There is also one hydrido ligand that is believed to bridge one of the Rh-Ge bonds. Compound 9 reacted with PPhMe(2) at 25 degrees C to give the tetraphosphine derivative Rh(8)(CO)(8)(PPhMe(2))(4)(mu(4)-GePh)(6), 11. The structure of 11 is similar to 9 except that a PPhMe(2) ligand has replaced a carbonyl ligand on each the four Rh(CO)(2) groups. Compound 10 reacted with CO at 68 degrees C to give the complex Rh(3)(CO)(6)(mu-GePh(2))(3)(mu(3)-GePh), 12. Compound 12 is formed by the loss of the hydrido ligand and the terminal GePh(3) ligand from 10 and the addition of one carbonyl ligand. All compounds were fully characterized by IR, NMR, elemental, and single-crystal X-ray diffraction analyses.     

Synthesis of novel platinum-silver and platinum-copper complexes with bridging alkynyl ligands

The study of the reactivity of [Pt₂M₄(CCR)₈] (M=Ag or cu; R=Ph or ^tBu) towards different neutral and anionic ligands is reported. This study reveals that reactions of the phenylacetylide derivatives [Pt₂M₄(CCPh)₈] with anionic, X⁻ (X=Cl or Br) or neutral donors (CN^tBu or py) in a molar ratio 1:4 (m/donor ratio 1:1) yield the trinuclear anionic (NBu₄)₂[{Pt(CCPh)₄ (MX)₂] (M=Ag or Cu, X =Cl or Br) or neutral [{Pt(CCPh0₄=sAGL)₂] (L=CN^tBu or py) complexes, respectively. The crystal structure of (NBu₄)₂[{Pt(CCPh)₄}(CuBr)₂](4) shows that the anion is formed by a dianionic Pt(CCPh)₄ fragment and two neutral CuBr units joined through bridging alkynyl ligands. All the alkynyl groups are σ bonded to Pt and η²-coordinated to a Cu atom which have an approximately trigonal-planar geometry. By contrast, similar reactions with [Pt₂M₄(CC^tBu)₈] (molar ratio M/donor 1:1) afford hexanuclear dianionic (NBu₄)₂[Pt₂M₄(CC^tBu)₈X₂] or neutral [Pt₂Ag₄(CC^tBu0₈Py₂]. Only by treatment with a large exces of Br ⁻ (molar ratio M/Br⁻ 1:2) are the trinuclear complexes (NBu₄)₂[{Pt(CC^tBu₄ (MBr)₂] (M=Ag, Cu) obtained. Attempted preparations of analogous complexes with phosphines (L′=PPh₃ or PEt₃) by reactions of [Pt₂M₄(CCR₈] with L′ leads to displacement of alkynyl ligands from platinum and formation of neutral mononuclear complexes [trans-Pt(CCR)₂L′₂].     

Dinuclear palladium(ii) complexes with bridging amidate ligands

New homonuclear dimeric Pd(ii) complexes have been synthesized by the reaction of Pd(en)(2+) or Pd(bipy)(2+) (where en = ethylenediamine and bipy = 2,2'-bipyridine) units with acetamide or by the Pd(ii) mediated hydrolysis of CH(3)CN. In these dimers the two metal centers are bridged by either two amidates or by the combination of one hydroxo group and one amidate ligand. The crystal structures of complexes {[Pd(bipy)](2)(micro-1,3-CH(3)CONH)(2)}(NO(3))(2).H(2)O.1/2(CH(3))(2)CO.1/2CH(3)CN () and {[Pd(bipy)](2)(micro-1,3-CH(3)CONH)(2)}(OTf)(2) () showed intrametallic Pd-Pd distances of 2.8480(8) A () and 2.8384(7) A (), respectively, in accordance with the accepted values for a strong Pd-Pd interaction. The presence of pi[dot dot dot]pi interactions between the bipyridine ligands on the di-micro-amidate complexes of Pd(bipy)(2+) shortens the distance between the two Pd centers and allows the formation of the metal-metal interaction. By contrast, the crystal structure of complex {[Pd(en)](2)(micro-1,3-CH(3)CONH)(2)}(OTf)(2).H(2)O (), (where OTf = triflate) where there is no pi[dot dot dot]pi interaction between the ligands on the metal centers, is also reported, and no Pd-Pd interaction is observed. Additionally, one of the complexes, {[Pd(en)](2)(micro-OH)(micro-CH(3)CONH)}(NO(3))(2) (), presents an interesting hydrogen bonded 3-D network formed by nitrate ions and water molecules. All complexes have been characterized by infrared and (1)H NMR spectroscopy.     

Preparation and characterization of conducting trimetallic nickel-dithiolene complexes with bridging tetrathiooxalate ligands

Trimetallic nickel dithiolene complexes with two tetrathiooxalate (tto) ligands were obtained by a reaction monitored by ESI-mass spectrometry followed by HPLC separation and were characterized by elemental or crystal structural analysis, MO calculations, and electrical conductivity measurements.     

New rhodium---ruthenium heterobimetallic complexes with bridging bi- or tri-dentate phosphine ligands

The mononuclear chelated complex [RuCl(Cp)(η²-dppa)] has been synthesised and reacted with [Rh₂Cl₂(CO)₄] to form the heterobimetallic complex [(Cp)Ru(μ-CO)₂{(μ-Ph₂PN(H)PPh₂}RhCl₂]. Complexes of [RuCl(Cp){(PPh₂)₂CHCH₂PPh₂}] have been reacted with [Rh₂Cl₂(CO)₄] or [RhCl(CO)₂(p-toluidene)]. Characterisation of these new ruthenium complexes was carried out using ³¹P-NMR, FAB mass spectroscopy, elemental analysis and IR spectrophotometry.     

Applications of ruthenium hydride borohydride complexes containing phosphinite and diamine ligands to asymmetric catalytic reactions

[reaction: see text] A series of novel trans-ruthenium hydride borohydride complexes with chiral phosphinite and diamine ligands were synthesized. They can be used in the asymmetric transfer hydrogenation of aryl ketones, including base-sensitive ones, to give chiral alcohols in moderate to good enantioselectivities (up to 94% ee). They are also efficient catalysts for the Michael addition of malonates to enones with enantioselectivities of up to 90%. This kind of catalyst allows a one-pot tandem Michael addition/H(2) hydrogenation protocol to build structures with multiple chiral centers.     

Heterodinuclear transition-metal complexes with multiple metal-metal bonds

Interactions between a pair of transition-metals can range from weak antiferromagnetic coupling to bonds of the highest multiplicity known in chemistry, for example, quadruple in isolatable compounds. Tremendous effort has been invested in studying homodinuclear transition-metal-metal bonds. In contrast, relatively little attention has been devoted to heterodinuclear analogues, as it is substantially more challenging to prepare and handle such entities. Yet, in this largely unexplored area of transition-metal chemistry, novel chemical interactions with unprecedented reactivities are likely to be found. Heterodinuclear analogues of diatomic transition-metal dimers being yet inaccessible, dinuclear complexes with Werner-type ligands provide examples of high-multiplicity bonds between different d elements in their least-perturbed form. Such compounds provide an opportunity to probe fundamental issues of chemical bonding between transition-metals, by revealing how and to what extent such bonds are affected by differences in the two metals. Complexes wherein electronically unsaturated heterodinuclear cores are stabilized by pi-acidic ligands (such as CO) hold the potential of new chemical reactions (including catalytic) that capitalize on the synergetic effect of two transition-metal centers.     

Rhodium(I) diolefin complexes with polycyclic π-arene ligands. Synthesis of bimetallic complexes with diphenylmethane as bridging ligand

Summary The preparation and properties of cationic arenerhodium(I) complexes of general formula [Rh(diolefin)(⁶arene)]ClO₄ (diolefin=1,5-cyclooctadiene, tetrafluorobenzobarrelene or trimethyltetrafluorobenzobarrelene; arene = biphenyl or diphenylmethane) are described. These complexes react with the solvated intermediate complex [Rh(diolefin)(Me₂CO)_x]ClO₄ to give homobimetallic [(diolefin)Rh(Ph₂CH₂)Rh(diolefin)](ClO₄)₂ derivatives. New heterobimetallic complexes of the type [(diolefin)Rh(Ph₂CH₂)Cr(CO)₃]ClO₄ have been synthesized by reaction of Cr(CO)₃(⁶-Ph₂CH₂) with the solvated complex [Rh(diolefin)(Me₂CO)_x]ClO₄ or, alternatively by treatment of [Rh(diolefin)(⁶-arene)]ClO₄ with the complex Cr(CO)₃(⁶Me₃B₃N₃Me₃) in chloroform solution.     

Phenyl-functionalized diiron propanediselenolato complexes containing intramolecular bridging diphosphine ligands

Reactions of [(μ-SeCH₂)₂CHC₆H₅]Fe₂(CO)₆ (A) with 1,1′-bis(diphenylphosphino)ferrocene (dppf) or 1,3-bis(diphenylphosphino)propane (dppp) in refluxing xylene yielded [(μ-SeCH₂)₂CHC₆H₅]Fe₂(CO)₄(μ-dppf) (1) or [(μ-SeCH₂)₂CHC₆H₅]Fe₂(CO)₄(μ-dppp) (2) in moderate yields. The chemical structures of both complexes were characterized by spectroscopic methods and X-ray crystallography, and the electronic structures were further investigated by UV–vis. The redox properties of both complexes in the absence and presence of acetic acid were observed by cyclic voltammetry (CV).     

Synthesis and properties of oligomers of iron-manganese carbonyl complexes with bridging disulfido ligands

The reactions of activated CpFeMn(CO)₇1a and Cp*FeMn(CO)₇1b, Cp=C₅Me₅ with thiirane yielded the new dimeric mixed metal disulfido complexes: [CpFeMn(CO)₅(μ₃-S₂)]₂ (2) and [Cp*FeMn(CO)₅(μ₃-S₂)]₂ (3). Compounds 2 and 3 both contain two triply bridging disulfido ligands. When heated at 40 °C, compound 2 was transformed into a trimeric compound Cp₃Fe₃Mn₃(CO)₁₅(μ₃-S₂)(μ₄-S₂)₂, 4. Compound 4 contains three disulfido ligands, each of which has a different bridging coordination mode in the six atom metal cluster. There are three inequivalent CpFe(CO)₂ groupings linked to a central Mn₃(S₂)₃ core by the disulfido ligands. In solution, compound 4 exhibits a dynamical intramolecular exchange process that interconverts two of the three CpFe(CO)₂ groups on the NMR timescale.     

Photochromic and redox properties of bisterpyridine ruthenium complexes based on dimethyldihydropyrene units as bridging ligands

We report herein the synthesis and characterization of four new bisterpyridine dinuclear ruthenium complexes containing the dimethyldihydropyrene (DHP) photochrome as bridging ligand. A synthetic strategy has been developed based on a Suzuki coupling reaction to synthesize these novel terpyridine-DHPs. The reactivity of these different ligands and dinuclear ruthenium complexes with light was examined by (1)H NMR and monitoring the changes in their absorption spectra upon irradiation at controlled wavelengths. The free ligands and their corresponding ruthenium complexes all displayed photochromic properties with highly efficient conversion between the closed stable isomers (DHP) and their open forms (CPD). The properties of the compounds in their closed and open forms were investigated by cyclic voltammetry, spectroscopy, and luminescence measurements.     

Dinuclear Schiff-base copper(II) complexes with various bridging groups

Three new centrosymmetric dinuclear copper(II) complexes, [Cu₂Cl₂(L¹)₂] (1), [Cu₂(μ _1,3-NCS)₂(L²)₂] (2), and [Cu₂(μ _1,1-N₃)₂(L³)₂] (3), where L¹, L², and L³ are the deprotonated forms of the Schiff bases 1-[(2-propylaminoethylimino)methyl]naphthalen-2-ol (HL¹), 1-[(3-methylaminopropylimino)methyl]naphthalen-2-ol (HL²), and 2-[(2-isopropylaminoethylimino)methyl]phenol (HL³), respectively, have been prepared and characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Each Cu is coordinated by the three donors of the Schiff bases and by two bridging groups, forming a square-pyramidal geometry.