Synthesis of Mixed Silylene–Carbene Chelate Ligands from N‐Heterocyclic Silylcarbenes Mediated by Nickel

The Ni^II‐mediated tautomerization of the N‐heterocyclic hydrosilylcarbene L²Si(H)(CH₂)NHC 1 , where L²=CH(C?CH₂)(CMe)(NAr)₂, Ar=2,6‐iPr₂C₆H₃; NHC=3,4,5‐trimethylimidazol‐2‐yliden‐6‐yl, leads to the first N‐heterocyclic silylene (NHSi)–carbene (NHC) chelate ligand in the dibromo nickel(II) complex [L¹Si:(CH₂)(NHC)NiBr₂] 2 (L¹=CH(MeC?NAr)₂). Reduction of 2 with KC₈ in the presence of PMe₃ as an auxiliary ligand afforded, depending on the reaction time, the N‐heterocyclic silyl–NHC bromo Ni^II complex [L²Si(CH₂)NHCNiBr(PMe₃)] 3 and the unique Ni⁰ complex [η²(Si‐H){L²Si(H)(CH₂)NHC}Ni(PMe₃)₂] 4 featuring an agostic Si? H→Ni bonding interaction. When 1,2‐bis(dimethylphosphino)ethane (DMPE) was employed as an exogenous ligand, the first NHSi–NHC chelate‐ligand‐stabilized Ni⁰ complex [L¹Si:(CH₂)NHCNi(dmpe)] 5 could be isolated. Moreover, the dicarbonyl Ni⁰ complex 6 , [L¹Si:(CH₂)NHCNi(CO)₂], is easily accessible by the reduction of 2 with K(BHEt₃) under a CO atmosphere. The complexes were spectroscopically and structurally characterized. Furthermore, complex 2 can serve as an efficient precatalyst for Kumada–Corriu‐type cross‐coupling reactions.     

Structural analysis of photo-oxidized (ethylenediamine)bis(2,2′-bipyridine)ruthenium(II) complexes by using on-line electrospray mass spectrometry of labeled compounds

Photo-oxidation of Ru(bpy)₂(en)²⁺, where bpy = 2,2′-bipyridine, en = ethylenediamine, was studied in isotopic labeling experiments by using on-line electrospray mass spectrometry (ESMS). The complex was known to undergo photochemical dehydrogenation of a fourelectron oxidation, giving the α,α′-diimine complexes in a stepwise manner via a two-electron-oxidized intermediate that represents loss of two hydrogen atoms from the en ligand. On-line mass analysis after photoirradiation (λ > 420 nm) of Ru(bpy)₂(ed)²⁺ (ed = ethylene-d₄diamine) showed that the ligand of the intermediate with loss of two hydrogen atoms was not an enamine but had an imine structure. Also, a ligand-oxygenated complex that has mass 14 amu higher than the Ru(bpy)₂(en)²⁺ complex was observed in the ES mass spectra. The ligand of this complex was proposed to have a nitroso structure as a primary product in ¹⁸O₂ experiments. The oxygenated complex was not generated in a stepwise manner via the imine intermediate, but directly by loss of two amino hydrogen atoms and addition of an oxygen atom. The source of the oxygen atom would be from oxygen dissolved in solution rather than from water in solution. Another oxygenated complex Ru(bpy)₂(NO ₂ ^#x2212; )⁺ was produced by irradiation and the structure was identified in ¹⁸O₂ experiments.     

Photo-induced oxidation of aqueous solution of Na2[Mo(V)2O4EDTA] in neutral KBr and K2S2O8 medium

When an aqueous solution of Na₂[Mo(V)₂O₄EDTA] (ethylene diamine tetraacetate) was photolyzed in the presence of excess KBr and K₂S₂O₈ at neutral pH, the complex was found to be oxidized due to the reactions of Br ₂ ^–. and SO ₄ ^–. , respectively. Oxidation of the complex was also observed due to the reactions of the complex with radiolytically generated Br ₂ ^–. and SO ₄ ^–. radicals. When the oxidation of the complex with SO ₄ ^–. was conducted in an unbuffered solution, a chain reaction was observed in the oxidation of the complex. The time resolved kinetics for the formation and decay of different transient intermediates and the relevant rate constants were investigated with a flash photolysis technique, and a probable mechanism for the oxidation process was given.     

Synthesis and Reactivity of an End‐Deck cyclo‐P4 Iron Complex

Reduction of the Fe^II complex [(^PhPP₂^Cy)FeCl₂] ( 2 ) generated an electron‐rich and unsaturated Fe⁰ species, which was reacted with white phosphorus. The resulting new complex, [(^PhPP₂^Cy)Fe(η⁴‐P₄)] ( 3 ), is the first iron cyclo‐P₄ complex and the only known stable end‐deck cyclo‐P₄ complex outside Group V. Complex 3 features an Fe^II center, as shown by Mössbauer spectroscopy, associated to a P₄^2? fragment. The distinct reactivity of complex 3 was rationalized by analysis of the molecular orbitals. Reaction of complex 3 with H⁺ afforded the unstable complex [(^PhPP₂^Cy)Fe(η⁴‐P₄)(H)]⁺ ( 4 ), whereas with CuCl and BCF, the complexes [(^PhPP₂^Cy)Fe(η⁴:η¹‐P₄)(μ‐CuCl)]₂ ( 5 ) and [(^PhPP₂^Cy)Fe(η⁴:η¹‐P₄)B(C₆F₅)₃] ( 6 ) were formed.     

Inner-sphere oxidation of cis-diaquabis(oxalato)chromate(III) by periodate in aqueous weakly acidic solutions

The kinetics of oxidation of cis-[Cr^III(ox)₂(H₂O)₂]^– (ox = C₂O₄ ^2–) by IO₄ ^– showed a first-order dependence on the initial Cr^III complex concentration in the presence of a vast excess of [IO₄ ^–]. The dependence of the pseudo-first-order rate constant on [IO₄ ^–] is complex and is consistent with the formation of a precursor complex. It is proposed that this complex is formed through the coordination of the two carbonyl oxygens of the ox ligand with the IO₄ ^– ion, forming a cyclic intermediate. The kinetics are consistent with the hydroxo form of the Cr^III complex being the reactive species, whereas the aqua species forms an unreactive complex.     

A new technetium(V)-2-thiohydantoin complex

Summary A new 2-thiohydantoin ^{99Tc v} complex was prepared by the direct reduction of TcO ₄ ^– with alkaline Na₂S₂O₄ in the presence of an excess of the ligand, and characterized by spectroscopy. Reversed phase HPLC on lichrosorb-Rp-18 showed the complex to be pure; electrophoresis measurements showed it to be neutral. The complex was H₂O soluble.     

Photochemistry in van der Waals complexes: Observation of the intermediate state of the Hg*,Cl2 reaction

A novel method designed to observe the collision complex of a photochemical reaction is reported here. The reactants Hg, Cl₂ are frozen in a van der Waals complex (HgCl₂), and then promoted by an optical excitation (250 nm) to the reactive state. The broad complex action spectrum, presumably due to the Hg⁺-Cl₂^? intermediate, is monitored through the HgCl(B ²Σ⁺) fluorescence.     

Syntheses,Structures, and Properties of Oxovanadium(V) Complexes with Ketone and Ketolate Ligands

VOCl₃ and Spiro(adamantan‐2, 2′‐homoadamantan‐3‐one) form a stable 1 : 1 complex, which has been isolated and characterised. A X‐ray structure analysis reveals a close V=O···H‐C contact supporting the presence of an analogous interaction leading to C‐H activation in the corresponding CrO₂Cl₂ complex. For both systems such geometrical arrangements are predicted by means of DFT calculations. The reaction of Spiro(adamantan‐2, 2′‐homoadamantan‐3‐one‐4‐olate), L² , with VOCl₃ leads to a complex [ L² ₂VOCl], which can be converted to the corresponding triflate [ L² ₂VO(O₃SCF₃)] via treatment with AgO₃SCF₃. The latter is a mononuclear oxovanadium(V) complex with a bulky ligand sphere where one coordination site is accessible (as the triflate ligand is quite loosely bound), and as it is furthermore soluble in organic solvents, it seems an interesting complex to start from in future experiments.     

The kinetics and thermodynamics of a novel efficient mixed water–1,4-dioxan solvent for the effective complexation of a neutral ruthenium complex with carbon monoxide at atmospheric pressure

Kinetic and thermodynamic investigations were performed for a mixed aqueous-organic, 1:1 (v/v) water–1,4-dioxane medium, which was found to be an efficient solvent for the interaction of a neutral dichlorotris(triphenylphosphine) ruthenium(II), RuCl₂(PPh₃)₃ complex with carbon monoxide at atmospheric pressure. During the interaction, RuCl₂(PPh₃)₃ dissociates to a neutral complex dichlorobis(triphenylphosphine) ruthenium(II), RuCl₂(PPh₃)₂, by losing a coordinated PPh₃ ligand and RuCl₂(PPh₃)₂ coordinates with CO to form an in situ carbonyl complex RuCl₂(CO)(PPh₃)₂. The in situ formed carbonyl complex RuCl₂(CO)(PPh₃)₂ was thoroughly characterized by equilibrium, spectrophotometric, IR, and electrochemical techniques. Under equilibrium conditions, the rate and dissociation constants for the dissociation of PPh₃ from RuCl₂(PPh₃)₃ were found to be favorable for the formation of the carbonyl complex RuCl₂(CO)(PPh₃)₂. The rates of complexation for the formation of RuCl₂(CO)(PPh₃)₂ were found to follow an overall second-order kinetics being first order in terms of the concentrations of both carbon monoxide and RuCl₂(PPh₃)₂. The determined activation parameters corresponding to the rate constant (ΔH^# = 35.9 ± 2.5 kJ mol⁻¹ and ΔS^# = −122 ± 6 J K⁻¹ mol⁻¹) and thermodynamic parameters corresponding to the formation constant (ΔH° = −33.5 ± 4.5 kJ mol⁻¹, ΔS° = −25 ± 8 J K⁻¹ mol⁻¹, and ΔG° = −25.7 ± 2.0 kJ mol⁻¹) were found to be highly favorable for the formation of the complex RuCl2(CO)(PPh3)2. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 359–369, 2008     

Interaction of Iodine with Hexaaza-18-crown-6 and Tetraaza-14-crown-4 in Chloroform Solution

Interactions of hexaaza-18-crown-6 (HA18C6) and tetraaza-14-crown-4 (TA14C4) with iodine have been investigated spectrophotometrically in chloroform solution. The observed time dependence of the charge-transfer band and subsequent formation of I₃ ^- in solution were related to the slow transformation of the initially formed 1:1 macrocycle. I₂ outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion, as follows: macrocycle + I₂→_fast ^K _f macrocycle.I₂ (outer complex) macrocycle.I₂ (outer complex) →^slow (macrocycle.I⁺)I^- (inner complex) macrocycle.I⁺)I^- (inner complex) + I²→^slow (macrocycle.I⁺)I₃ ^-. The pseudo-first-order rate constants at various temperatures for thetransformation process were evaluated from the absorbance-time data. The activation parameters (E_a, Δ H^?, and Δ S^?) for thetransformation were obtained from the temperature dependence of the rate constants. The stoichiometry and formation constants of the resulting EDA complexes have also been determined. It was found that the (TA14C4.I⁺)I₃ ^- is more stable the (HA18C6.I⁺)I₃ ^- complex in chloroform solution.     

A cis‐Divacant Octahedral and Mononuclear Iron(IV) Imide

A rare, low‐spin Fe^IV imide complex [(pyrr₂py)Fe?NAd] (pyrr₂py^2?=bis(pyrrolyl)pyridine; Ad=1‐adamantyl) confined to a cis‐divacant octahedral geometry, was prepared by reduction of N₃Ad by the Fe^II precursor [(pyrr₂py)Fe(OEt₂)]. The imide complex is low‐spin with temperature‐independent paramagnetism. In comparison to an authentic Fe^III complex, such as [(pyrr₂py)FeCl], the pyrr₂py^2? ligand is virtually redox innocent.     

Enzyme Design from the Bottom Up: An Active Nickel Electrocatalyst with a Structured Peptide Outer Coordination Sphere

Catalytic, peptide‐containing metal complexes with a well‐defined peptide structure have the potential to enhance molecular catalysts through an enzyme‐like outer coordination sphere. Here, we report the synthesis and characterization of an active, peptide‐based metal complex built upon the well‐characterized hydrogen production catalyst [Ni(P^Ph₂N^Ph)₂]²⁺ (P^Ph₂N^Ph=1,3,6‐triphenyl‐1‐aza‐3,6‐diphosphacycloheptane). The incorporated peptide maintains its β‐hairpin structure when appended to the metal core, and the electrocatalytic activity of the peptide‐based metal complex (≈100,000 s^?1) is enhanced compared to the parent complex ([Ni(P^Ph₂N^APPA)₂]²⁺; ≈50,500 s^‐1). The combination of an active molecular catalyst with a structured peptide provides a scaffold that permits the incorporation of features of an enzyme‐like outer‐coordination sphere necessary to create molecular electrocatalysts with enhanced functionality.     

Preparation,properties and x-ray crystal structure of a complex of bis(triphenylphosphoranylidene)ammonium iodide with 7,7,8,8-tetracyano-P-quinodimethane: (PPN)2(TCNQ)3(CH3CN)2

Bis(triphenylphosphoranylidene)ammonium iodide (PPN⁺I^?) forms a 2:3 complex with TCNQ [(PPN)₂(TCNQ)₃(CH₃CN)₂] that provides an example of a TCNQ complex containing acetonitrile in the crystal lattice; the material is a semi-conductor with trimerised TCNQ stacks.     

A one-pot method to prepare the carbene complex [TpRhCl2(CHNiPr2)] from [TpRh(CO)2], CHCl3, and NHiPr2

The complex [Tp^Me₂,ClRh(CO)₂] reacts with chloroform to give quantitatively the rhodium(III) complex [Tp^Me₂,ClRhCl(CHCl₂)(CO)] resulting from the oxidative addition of a C-Cl bond. Further reaction with diisopropylamine gives the aminocarbene complex [Tp^Me₂,ClRhCl₂(CHNiPr₂)], whose X-ray crystal structure has been solved. Addition of an excess of diisopropylamine to [Tp^Me₂,ClRh(CO)₂] in chloroform provides directly [Tp^Me₂,ClRhCl₂(CHNiPr₂)].     

Heteroleptic Square Planar Cobalt(I/II) Complexes

Reduction of the cobalt(II) chloride complex, Ph₂B(^tBuIm)₂Co(THF)Cl ( 1 ) in the presence of ^tBuN≡C affords the diamagnetic, square planar cobalt(I) complex Ph₂B(^tBuIm)₂Co(C≡N^tBu)₂ ( 2 ). This is a rare example of a 16-electron cobalt(I) complex that is structurally related to square planar noble metal complexes. Accordingly, the electronic structure of 2 , as calculated by DFT, reveals that the HOMO is largely d_z² in character. Complex 2 is readily oxidized to its cobalt(II) congener [Ph₂B(^tBuIm)₂Co(C=N^tBu)₂]BPh₄ ( 3 -BPh₄), whose EPR spectral parameters are characteristic of low-spin d⁷ with an unpaired electron in an orbital of d_z² parentage. This is also consistent with the results of DFT calculations. Despite its 16-electron configuration and the d_z² parentage of the HOMO, the only tractable reactions of 2 involve one electron oxidation to afford 3 .     

2,2′-Bipyridyl formation from 2-arylpyridines through bimetallic diyttrium intermediate

An alkylyttrium complex supported by an N,N′-bis(2,6-diisopropylphenyl)ethylenediamido ligand, (ArNCH₂CH₂NAr)Y(CH₂SiMe₃)(THF)₂ (1, Ar = 2,6-ⁱPr₂C₆H₃), activated an ortho-phenyl C–H bond of 2-phenylpyridine (2a) to form a (2-pyridylphenyl)yttrium complex (3a) containing a five-membered metallacycle. Subsequently, a unique C(sp²)–C(sp²) coupling of 2-phenylpyridine proceeded through a bimetallic yttrium intermediate, derived from an intramolecular shift of the yttrium center to an ortho-position of the pyridine ring in 3a, to yield a bimetallic yttrium complex (4a) bridged by two-electron reduced 6,6′-diphenyl-2,2′-bipyridyl. Aryl substituents at the ortho-position of the pyridine ring were key in order to destabilize the μ,κ²-(C,N)-pyridyldiyttrium intermediate prior to the C(sp²)–C(sp²) bond formation.     

Synthesis,crystal structure,and fluorescence of an unexpected dialkoxo-bridged dinuclear copper(II) complex with bis(salen)-type tetraoxime

An unexpected dinuclear Cu(II) complex, [Cu₂(L²)₂] (H₂L^2?=?3-methoxysalicylaldehyde O-(2-hydroxyethyl)oxime), has been synthesized via complexation of Cu(II) acetate monohydrate with H₄L¹. Catalysis by Cu(II) results in unexpected cleavage of two N–O bonds in H₄L¹, giving a dialkoxo-bridged dinuclear Cu(II) complex possessing a Cu–O–Cu–O four-membered ring core instead of the usual bis(salen)-type tetraoxime Cu₃–N₄O₄ complex. Every complex links six other molecules into an infinite-layered supramolecular structure via 12 intermolecular C–H?···?O hydrogen bonds. Furthermore, Cu(II) complex exhibits purple emission with maximum emission wavelength λ_max?=?417?nm when excited with 312?nm.     

On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen,Ni(N2)2

The electronic ground and excited states of the coordinatively unsaturated complex Ni(η¹‐N₂)₂, isolated in an Ar matrix, are analyzed in detail by vibrational and electronic absorption and emission spectroscopies allied with quantum chemical calculations. The bond force constants are determined from a normal coordinate analysis and compared with those of the isoelectronic carbonyl complex. The consequences for the bond properties are discussed, and the trend in the force constants is compared with the standard formation enthalpies. The linear complex Ni(η¹‐N₂)₂ with two terminal dinitrogen ligands can be photoisomerized to two isomeric, metastable forms Ni(η¹‐N₂)(η²‐N₂) and Ni(η²‐N₂)₂, with one and two side‐on coordinated dinitrogen ligands, respectively.     

Synthesis,crystal structure and magnetic characterization of a novel linear trinuclear copper(II) complex bridged by phenoxy and benzyloxy oxygen atoms

A novel linear trinuclear copper(II) complex bridged by phenoxy and benzyloxy oxygen atoms ([Cu₃L₂](ClO₄)₂ · (CH₃CN)₂, L = C₁₁H₁₃BrN₂O₂ ²⁻) was synthesized and the crystal structure of the complex was determined by X-ray diffraction technique. The crystal structure of the complex contains a linear trinuclear array of copper(II) ions in which the central copper(II) ion is in an octahedron coordination sphere and lies on an inversion center of the molecule, the terminal ones are in an identical square pyramid structure. Variable-temperature magnetic data indicate that the complex displays a strong antiferromagnetic coupling with J = −270(8) cm⁻¹ between the metal ions.