Tuning the potential of redox-active diphosphine ligands based on the alkyne complexes [Tp*W(CO)L{η2-C2(PPh2)2}].

Eleven complexes with the general formula [Tp*W(CO)L{η2-C2(PPh2)2}]n+ {Tp* = hydridotris(3,4,5-trimethylpyrazolyl)-borate, L = F-, Cl-, Br-, I-, MeS-, PhS-, pyCH2S-, CN- and TfO-; n = 0 and L = CH3CN and pyridine; n = 1} have been synthesized and fully characterized. Depending on L, the oxidation process from W(II) to W(III) is detected between -0.28 and +0.55 V vs. Fc/Fc+ and the spectroscopic properties (X-ray, IR, and NMR) are influenced according to the electron-rich or electron-poor character of the central metal. The basicity of the alkyne complex-based phosphine groups was estimated by the 31P/77Se coupling method of the corresponding diselenides. Selected examples of the dppa-complex ligands were converted into the corresponding κ2-PdCl2 chelate complexes and employed in a Sonogashira reaction in order to estimate the effect of L on the catalytic behaviour of the dinuclear complexes. While the spectroscopic properties show a good correlation with the redox potential in a mostly linear fashion, catalytic activity is influenced only slightly. The effect of PdCl2 coordination on the alkyne complex is evident from the W(II)/W(III) redox potentials measured by cyclic voltammetry supported by a change of the CO stretching frequency in IR. A comparison of the molecular structures of the alkyne complexes with terminal phosphine groups and the PdCl2 chelate complexes all determined by XRD shows the essential flexibility of the bend-back angles in the alkyne complex moiety.

Synthesis and coordination behaviour of 1H-1,2,3-triazole-4,5-dithiolates.

The preparative access to and first group 10 metal complexes of novel 1H-1,2,3-triazole-4,5-dithiolate ligands (tazdt2-) are reported. A set of S-protected 1H-1,2,3-triazole-4,5-dithiol derivatives with R1 = 2,6-dimethylphenyl (Xy) or benzyl (Bn) at N1 and with R2 = Bn or trimethylsilylethyl (TMS-ethyl) at both S atoms were synthesized by a 1,3-dipolar cycloaddition catalysed by either Ru(II) or Cu(I). Extensive investigations on the removal of the protective groups resulted the reductive removal of benzyl groups to be superior in isolating the free 4,5-dithiols of R1N3C2(SH)2 with R1 = Xy (H2-8) or Bn (H2-9). Coordination of these ligands led to the formation of the metal complexes [(η5-C5H5)2Ti(8)], [Ni(dppe)(8)], [Ni(dppe)(9)], [Pd(dppe)(9)] {dppe = bis(diphenylphosphanyl)ethane} and homoleptic (NBu4)n[Ni(8)2] (n = 1, 2). All complexes were fully characterized including structure determination by single crystal XRD. The electronic properties of the Ni and Pd complexes were determined by cyclic voltammetry, UV/vis and EPR spectroscopy supported by DFT calculations. According to the spectral and electrochemical data, the tazdt2- complexes resemble the corresponding benzene-1,2-dithiolate (bdt2-) type compounds reflecting the restricted influence of the electron-withdrawing N3 moiety in the backbone. DSC-TGA measurements with [(η5-C5H5)2Ti(8)] and [Ni(dppe)(8)] indicate a well-defined thermal process involving simultaneous elimination of both N2 and CS.

Pseudo-Octahedral Iron(II) Complexes with Near-Degenerate Charge Transfer and Ligand Field States at the Franck-Condon Geometry.

Increasing the metal-to-ligand charge transfer (MLCT) excited state lifetime of polypyridine iron(II) complexes can be achieved by lowering the ligand's π* orbital energy and by increasing the ligand field splitting. In the homo- and heteroleptic complexes [Fe(cpmp)2 ]2+ (12+ ) and [Fe(cpmp)(ddpd)]2+ (22+ ) with the tridentate ligands 6,2''-carboxypyridyl-2,2'-methylamine-pyridyl-pyridine (cpmp) and N,N'-dimethyl-N,N'-di-pyridin-2-ylpyridine-2,6-diamine (ddpd) two or one dipyridyl ketone moieties provide low energy π* acceptor orbitals. A good metal-ligand orbital overlap to increase the ligand field splitting is achieved by optimizing the octahedricity through CO and NMe units between the coordinating pyridines which enable the formation of six-membered chelate rings. The push-pull ligand cpmp provides intra-ligand and ligand-to-ligand charge transfer (ILCT, LL'CT) excited states in addition to MLCT excited states. Ground and excited state properties of 12+ and 22+ were accessed by X-ray diffraction analyses, resonance Raman spectroscopy, (spectro)electrochemistry, EPR spectroscopy, X-ray emission spectroscopy, static and time-resolved IR and UV/Vis/NIR absorption spectroscopy as well as quantum chemical calculations.

Development and application of redox-active cyclometallating ligands based on W(II) alkyne complexes.

The assembly of dinuclear complexes with the ultimate smallest ditopic ligands based on side-on complexes of methyl substituted alkynes is presented. In fact, the coordination of Ru(II) and Ir(III) by a W alkyne complex based cyclometallating metalla-ligand causes close intermetallic electronic cooperation, which substantially changes the electrochemical and photophysical properties of the single isolated moieties.

Transient FTIR spectroscopy after one- and two-colour excitation on a highly luminescent chromium(III) complex.

The development of photoactive transition metal complexes with Earth-abundant metals is a rapidly growing research field, where a deeper understanding of the underlying photophysical processes is of great importance. A multitude of potential applications in the fields of photosensitizing, optical sensing, photoluminescence and photoredox catalysis motivates demanding spectroscopic studies. We applied a series of high-level spectroscopic methods on the previously reported highly luminescent chromium(iii) complex [Cr(ddpd)2](BF4)3 (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine) possessing two near-IR emissive doublet states with microsecond lifetimes. Luminescence measurements were performed at temperatures down to about 10 K, showing a remarkable rise of the integrated emission intensity by more than a factor of three. The emissive doublet states were structurally characterized by transient FTIR spectroscopy at 290 K and 20 K, supplemented by ground state FTIR and Raman spectroscopy in combination with density functional theory. According to emission and step-scan FT-IR spectroscopy, the stronger luminescence at lower temperature arises from decreased non-radiative decay via energy transfer to CH vibrational overtones and increased radiative decay based on lowered symmetry. Pump/pump/probe (FTIR) and pump/dump/probe (FTIR) schemes were developed to modulate the excited doublet state populations at 290 and 20 K as a function of specific near-IR pump vs. dump wavelengths. The effect of the second near-IR pulse can be explained by combinations of excited state absorption, ground state absorption and stimulated emission. The successful establishment of these two-colour step-scan FTIR experiments is an important step towards profound studies on further transition metal complexes with energetically close-lying excited states in the near future.

Migratory insertion of isocyanide into a ketenyl-tungsten bond as key step in cyclization reactions.

Treatment of the side-on tungsten alkyne complex of ethinylethyl ether [Tp*W(CO)2(η2-C,C'-HCCOCH2CH3)]+ {Tp* = hydridotris(3,4,5-trimethylpyrazolyl)borate} (2a) with n-Bu4NI afforded the end-on ketenyl complex [Tp*W(CO)2(κ1-HCCO)] (4a). This formal 16 ve complex bearing the prototype of a ketenyl ligand is surprisingly stable and converts only under activation by UV light or heat to form a dinuclear complex [Tp*2W2(CO)4(µ-CCH2)] (6). The ketenyl ligand in complex 4a underwent a metal template controlled cyclization reaction upon addition of isocyanides. The oxametallacycles [Tp*W(CO)2{κ2-C,O-C(NHXy)C(H)C(Nu)O}] {Nu = OMe (7), OEt (8), N(i-Pr)2 (9), OH (10), O1/2 (11)} were formed by coordination of Xy-NC (Xy = 2,6-dimethylphenyl) at 4a and subsequent migratory insertion (MI) into the W-ketenyl bond. The resulting intermediate is susceptible to addition reactions with protic nucleophiles. Compounds 2a-PF6, 4a/b, and 7-11 were fully characterized including XRD analysis. The cyclization mechanism has been confirmed both experimentally and by DFT calculations. In cyclic voltammetry, complexes 7-9 are characterized by a reversible W(ii)/W(iii) redox process. The dinuclear complex 11 however shows two separated redox events. Based on cyclic voltammetry measurements with different conducting electrolytes and IR spectroelectrochemical (SEC) measurements the W(ii)/W(iii) mixed valent complex 11+ is assigned to class II in terms of the Robin-Day classification.

Metal/Metal Redox Isomerism Governed by Configuration.

A pair of diastereomeric dinuclear complexes, [Tp'(CO)BrW{µ-η2 -C,C'-κ2 -S,P-C2 (PPh2 )S}Ru(η5 -C5 H5 )(PPh3 )], in which W and Ru are bridged by a phosphinyl(thiolato)alkyne in a side-on carbon P,S-chelate coordination mode, were synthesized, separated and fully characterized. Even though the isomers are similar in their spectroscopic properties and redox potentials, the like-isomer is oxidized at W while the unlike-isomer is oxidized at Ru, which is proven by IR, NIR and EPR-spectroscopy supported by spectro-electrochemistry and computational methods. The second oxidation of the complexes was shown to take place at the metal left unaffected in the first redox step. Finally, the tipping point could be realized in the unlike isomer of the electronically tuned thiophenolate congener [Tp'(CO)(PhS)W{µ-η2 -C,C'-κ2 -S,P-C2 (PPh2 )S}Ru(η5 -C5 H5 )-(PPh3 )], in which valence trapped WIII /RuII and WII /RuIII cationic species are at equilibrium.

Facile Synthesis of a Stable Side-on Phosphinyne Complex by Redox Driven Intramolecular Cyclisation.

Alkyne complexes with vicinal substitution by a Lewis acid and a Lewis base at the coordinated alkyne are prospective frustrated Lewis pairs exhibiting a particular mutual distance and, hence, a specific activation potential. In this contribution, investigations on the generation of a WII alkyne complex bearing a phosphine as Lewis base and a carbenium group as Lewis acid are presented. Independently on potential substrates added, an intramolecular cyclisation product was always isolated. A subsequent deprotonation step led to an unprecedented side-on λ5 -phosphinyne complex, which is interpreted as highly zwitterionic according to visible absorption spectroscopy supported by TD-DFT. Low-temperature 31 P NMR and EPR spectroscopic measurements combined with time-dependent IR-spectroscopic monitoring provided insights in the mechanism of the cyclisation reaction. Decomposition of the multicomponent IR spectra by multivariate curve resolution and a kinetic hard-modelling approach allowed the derivation of kinetic parameters. Assignment of the individual IR spectra to potential intermediates was provided by DFT calculations.

Pathways to Polynuclear Complexes with α-S,N-Substituted Alkynes as Bridging Ligands.

Recently, alkyne complexes with terminal thiolate/amide substitution have been shown to act as S,N-chelate ligands in dinuclear complexes. In this study, the detailed synthesis and reactivity of W(II) alkyne complexes bearing different amino groups in the α-position are reported. The preparative scheme starts with cationic alkyne complexes [Tp'W(CO)2-η2-C,C'-C2Br(SR)]PF6 {Tp' = hydridotris(3,5-dimethylpyrazolyl)borate, R = benzyl (Bn), C2H4SiMe3}, which are obtained by applying free bromo alkynes. Subsequent nucleophilic substitution of the bromine substituent led to unsymmetrical substituted alkyne complexes [Tp'W(CO)2-η2-C,C'-C2(SR)(NHBn)]PF6 with S,N substitution in the α position of the coordinated alkyne. Depending on the base used, deprotonation of the secondary amine resulted in either neutral iminoketenyl complexes [Tp'W(CO)2-η2-C,C'-C2(SR)(NBn)] or a zwitterionic PF5 adduct. Reductive removal of the benzyl protective group was primarily observed at the imine substituent, causing a side-on/end-on rearrangement to the cyanide substituted carbene complex K[Tp'W(CO)2-η1-C(CN)(SBn)]. The reversibility of the rearrangement was proven with HBF4/Et2O, because double protonation led to [Tp'W(CO)2-η2-C,C'-C2(SR)(NH2)]BF4 exhibiting an unprecedented primary amine substitution at the coordinated alkyne. The reaction sequence starting with the thiol SC2H4SiMe3 derivative leading to the desired [Tp'W(CO)2-η2-C,C'-C2S(NHBn)] with a terminal S atom as well as the bonding situation in those complexes is discussed based on full spectroscopic characterization including X-ray structure analyses. Finally, a trinuclear complex assembled by homoleptic coordination of Pd(II) by two anionic S,N-chelates [Tp'W(CO)2-η2-C,C'-C2S(NBn)]- is presented.

Effect of subgroup-specific multimodal therapy on chronic spinal back pain and function-a prospective inpatient multicentre clinical trial in Germany.

Treatment modalities of spinal pain patients are discussed diversely, and different multimodal therapy programs have been developed. Purpose of the present study was to evaluate therapy outcome and effectiveness of an inpatient interdisciplinary and multimodal treatment program.This prospective multicentre clinical trial has been performed with patients from orthopedic hospitals receiving a functional musculoskeletal therapy pathway. Outcome measures were pain intensity and back-specific function (Oswestry Disability Index) before (T1) and after the intervention (T2) as well as after 6 and 12 months (T3, T4). Statistical approach included parametric (t test) and nonparametric (Wilcoxon-test) tests and the calculation of effect sizes. Additionally, a statistical subgroup analysis based on selected parameters (degree of pain chronicity, gender, and age) was performed using linear mixed models.In total, 249 patients (42.6% men, 57.4% women) with spinal pain were included, 133 patients were accessible for follow-up at T3 and 106 patients at T4.Average pain (AP) reduced significantly (P <.001) from T1 to T4 with an effect size of 0.99. Back-specific function also improved (P <.001) over all measuring time points (TP) (effect size: 0.63). Furthermore, the statistical subgroup analysis demonstrated the efficacy of the treatment concept within the subgroup parameters chronicity degree and age.A functional musculoskeletal therapy pathway including treatment of musculoskeletal dysfunctions appears to be beneficial in terms of treating pain and function. Pain chronicity and age seems to be factors influencing therapy outcome. Further studies are needed to examine the superiority of these inpatient programs for back pain including control groups.

Ultrafast Energy Transfer in Dinuclear Complexes with Bridging 1,10-Phenanthroline-5,6-Dithiolate.

We report herein the preparation and characterization of dinuclear complexes with the bridging ligand 1,10-phenanthroline-5,6-dithiolate (phendt2-) bearing Ru(bpy)2 or Ir(ppy)2 at the diimine moiety and Ni(dppe), Ni(dppf), CoCp, RhCp*, and Ru( p-Me-iPr-benzene) at the dithiolate unit. In comparison with the mononuclear precursors used in the synthesis, all dinuclear complexes were characterized by absorption and photoluminescence spectroscopy as well as cyclic voltammetry. Because of the beneficial spectral and electrochemical properties of the Ir/Co complex for a light-driven charge separation, this complex was investigated in detail by time-resolved luminescence {nanosecond (ns)-resolution} and transient absorption spectroscopy {femtosecond (fs)-resolution}. All measurements supported by DFT calculations show that the observed effective luminescence quenching by the dithiolate coordinated metal is caused by an ultrafast singlet-singlet Dexter energy transfer.

Sterically encumbered metalla-diphosphines: unlocking alkyne rotation by PtII coordination.

We present the synthesis and coordination chemistry of a series of WII alkyne complexes with symmetric and asymmetric acetylene diphosphines. Chelate-like P,P'-coordination of PtCl2 cause a drastic potential change of the W centered oxidation proving intermetallic cooperativity. The choice of peripheric P-substituents has a measurable influence on the potential itself as well on the respective potential change upon coordination. The enlarged deviation of the diphosphino alkyne from linearity in the dinuclear complexes unlock alkyne rotation making different isomers accessible.

Synthesis and activation potential of an open shell diphosphine.

A paramagnetic WIII alkyne complex bearing free terminal diphenylphosphino groups at the side-on coordinated alkyne was synthesized using a stepwise template strategy. This moderately stable metal supported open shell diphosphine shows an unprecedented spontaneous splitting of nitric oxide providing a WII-η2-C2{P(NH2)Ph2}{P(O)Ph2}+ complex featuring an amino phosphonium and a phosphine oxide substituent.

Minimalistic Ditopic Ligands: An α-S,N-Donor-Substituted Alkyne as Effective Intermetallic Conjugation Linker.

The capability of donor-substituted alkynes to link different metal ions in a side-on carbon donor-chelate coordination mode is extended from the donor centers S and P to the second period element N. The complex [Tp'W(CO)2 {η(2) -C2 (S)(NHBn)}] (Tp'=hydrido-tris(3,5-dimethylpyrazolyl)borate, Bn=benzyl) bearing a terminal sulfur atom and a secondary amine substituent is accessible by a metal-template synthesis. Subsequent deprotonation allowed the formation of remarkably stable heterobimetallic complexes with the [(η(5) -C5 H5 )Ru(PPh3 )] and the [Ir(ppy)2 ] moiety. Electrochemical and spectroscopic investigations (cyclic voltammetry, IR, UV/Vis, luminescence, EPR), as well as DFT calculations, and X-ray structure determinations of the W-Ru complex in two oxidation states reveal a strong metal-metal coupling but also a limited delocalization of excited states.

Dual nucleophilic substitution at a W(ii) η(2)-coordinated diiodo acetylene leading to an amidinium carbyne complex.

The synthesis and reactivity of a W(ii) C2I2 complex towards various nucleophiles are described. Soft, aprotic nucleophiles like 4-dimethylaminopyridine (DMAP) lead to substitution of one CO at tungsten, whereas reaction with an excess of benzylamine results in a dual nucleophilic substitution at the alkyne moiety involving the rearrangement to a novel cationic amidinium carbyne complex.

Understanding the Excited State Behavior of Cyclometalated Bis(tridentate)ruthenium(II) Complexes: A Combined Experimental and Theoretical Study.

The synthesis and characterization of the donor-acceptor substituted cyclometalated ruthenium(II) polypyridine complex isomers [Ru(dpb-NHCOMe)(tpy-COOEt)](PF6) 1(PF6) and [Ru(dpb-COOEt)(tpy-NHCOMe)](PF6) 2(PF6) (dpbH = 1,3-dipyridin-2-ylbenzene, tpy = 2,2';6,2"-terpyridine) with inverted functional group pattern are described. A combination of resonance Raman spectroscopic and computational techniques shows that all intense visible range absorption bands arise from mixed Ru → tpy/Ru → dpb metal-to-ligand charge transfer (MLCT) excitations. 2(PF6) is weakly phosphorescent at room temperature in fluid solution and strongly emissive at 77 K in solid butyronitrile matrix, which is typical for ruthenium(II) polypyridine complexes. Density functional theory calculations revealed that the weak emission of 2(PF6) arises from a (3)MLCT state that is efficiently thermally depopulated via metal-centered ((3)MC) excited states. The activation barrier for the deactivation process was estimated experimentally from variable-temperature emission spectroscopic measurements as 11 kJ mol(-1). In contrast, 1(PF6) is nonemissive at room temperature in fluid solution and at 77 K in solid butyronitrile matrix. Examination of the electronic excited states of 1(PF6) revealed a ligand-to-ligand charge-transfer ((3)LL'CT) as lowest-energy triplet state due to the very strong push-pull effect across the metal center. Because of the orthogonality of the participating ligands, emission from the (3)LL'CT is symmetry-forbidden. Hence, in this type of complex a stronger push-pull effect does not increase the phosphorescence quantum yields but completely quenches the emission.

A new class of azadipnictiridines generated by an unusual rearrangement reaction.

Dipnictadiazanediyls, [E(µ-NR)]2 (E = P, As), the pnictogen analogues of cyclobutandiyl, were found to react readily with alkynes forming [2.1.1]bicyclic structures. These, in turn, rearrange in an unprecedented reaction to [3.1.o]bicycles leading to the isolation of the first azadiarsiridine and the determination of its solid-state structure. All new species were comprehensively characterized, and the reaction pathways and bonding situations were computationally studied.

Dinuclear Ru/Ni, Ir/Ni, and Ir/Pt complexes with bridging phenanthroline-5,6-dithiolate: synthesis, structure, and electrochemical and photophysical behavior.

We report the synthesis and full characterization of dinuclear complexes with the bridging ligand phenanthroline-5,6-dithiolate (phendt(2-)) featuring the [Ru(bpy)2](2+) or Ir(ppy)2](+) fragment at the diimine donor center and the [Ni(dppe)](2+) or [Pt(phen)](2+) complex moiety at the dithiolate group. The molecular structures of the mononuclear complexes [(C5H5)2Ti(S,S'-phendt)] and [(ppy)2Ir{N,N'-phendt-(C2H4CN)2}](PF6) as well as the dinuclear complex [(C5H5)(PPh3)Ru(phendt)Ni(dppe)](PF6) determined by X-ray diffraction (XRD) studies are compared. Photophysical studies with mononuclear [(bpy)2Ru{phendt-(C2H4CN)2}](2+) and [(ppy)2Ir{phendt-(C2H4CN)2}](+) as well as dinuclear [(bpy)2Ru(phendt)Ni(dppe)](2+) and [(ppy)2Ir(phendt)Ni(dppe)](+) uncovered an effective luminescence quenching in the dinuclear complexes. Lifetime measurements at room temperature, steady-state measurements at low temperature, electrochemical investigations, and DFT calculations provide evidence for a very efficient energy transfer from the Ru/Ir to the Ni complex moiety with a rate constant k > 5 × 10(9) s(-1). In comparison, the [Ru]phendt[Ni] complex displays a higher quenching efficiency with reduced excited state lifetime, whereas the [Ir]phendt[Ni] complex is characterized by an unaltered lifetime of the thermally equilibrated excited state.

Acetylene dithiolate linking up the [Tp'W(CO)(CN)] moiety with Ru(II) or Pd(II.).

A series of heterodinuclear complexes with acetylene dithiolate (acdt(2-) ) as the bridging moiety were synthesised by a facile one-pot procedure that avoided use of the highly elusive acetylene dithiol. Generation of the W-Ru complex [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] (Tp'=hydrotris(3,5-dimethylpyrazolyl)borate) and the W-Pd complexes [Tp'W(CN)(CO)(C2 S2 )Pd(dppe)] and [Tp'W(CO)2 (C2 S2 )Pd(dppe)][PF6 ] (dppe=1,2-bis(diphenylphoshino)ethane), which exhibit a [W(η(2) -κ(2) -C2 S2 )M] core (M=Ru, Pd), was accomplished by using a transition-metal-assisted solvolytical removal of the Me3 Si-ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured W-Ru complex [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] shows reversible redox chemistry, as does the prototype complex [Tp'W(CO)2 (C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )][PF6 ]. Single crystal X-ray diffraction and IR, EPR and UV/Vis spectroscopic studies in conjunction with DFT calculations prove the high electronic delocalisation of states over the acdt(2-) linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt(2-) in [Tp'W(CN)(CO)(C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )] relative to [Tp'W(CO)2 (C2 S2 )Ru(η(5) -C5 H5 )(PPh3 )](+) . In addition, the influence of the overall complex charge on the metric parameters was investigated by single-crystal X-ray diffraction studies with the W-Pd complexes [Tp'WL2 (C2 S2 )Pd(dppe)] (L=(CN(-) )(CO) or (CO)2 ). The central [W(C2 S2 )Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals.