Synthesis, structure and dynamics of NHC-based palladium macrocycles

A series of macrocyclic CNC pincer pro-ligands based on bis(imidazolium)lutidine salts with octa-, deca- and dodecamethylene spacers have been prepared and their coordination chemistry investigated. Using a Ag2O based transmetallation strategy, cationic palladium(II) chloride complexes [PdCl{CNC–(CH2)n}][BArF4] (n = 8, 10, 12; ArF = 3,5-C6H3(CF3)2) were prepared and fully characterised in solution, by NMR spectroscopy and ESI-MS, and in the solid-state, by X-ray crystallography. The smaller macrocyclic complexes (n = 8 and 10) exhibit dynamic behaviour in solution, involving ring flipping of the alkyl spacer across the Pd–Cl bond, which was interrogated by variable temperature NMR spectroscopy. In the solid-state, distorted coordination geometries are observed with the spacer skewed to one side of the Pd–Cl bond. In contrast, a static C2 symmetric structure is observed for the dodecamethylene based macrocycle. For comparison, palladium(II) fluoride analogues [PdF{CNC–(CH2)n}][BArF4] (n = 8, 10, 12) were also prepared and their solution and solid-state structures contrasted with those of the chlorides. Notably, these complexes exhibit very low frequency 19F chemical shifts (ca. −400 ppm) and the presence of C–HF interactions (2hJFC coupling observed by 13C NMR spectroscopy). The dynamic behaviour of the fluoride complexes is largely consistent with the smaller ancillary ligand; [PdF{CNC–(CH2)8}][BArF4] exceptionally shows C2v time averaged symmetry in solution at room temperature (CD2Cl2, 500 MHz) as a consequence of dual fluxional processes of the pincer backbone and alkyl spacer

Coordination chemistry of a calix[4]arene-based NHC ligand : dinuclear complexes and comparison to IiPr2Me2

The preparation and coordination chemistry of 5,17-bis(3-methyl-1-imidazol-2-ylidene)-25,26,27,28-tetrapropoxycalix[4]arene (1) is described. Starting from the bis(imidazolium) pro-ligand 1·2HI, the free carbene 1 was readily generated in solution through deprotonation using K[OtBu] and its reactivity with rhodium(I) dimers [Rh(COD)Cl]2 (COD = 1,5-cyclooctadiene) and [Rh(CO)2Cl]2 investigated. Dinuclear complexes were isolated in both cases, where the calix[4]arene-based NHC ligand adopts a bridging μ2-coordination mode, and in one case characterised in the solid-state by X-ray diffraction. Using instead an isolated and well-defined (mononuclear) silver transfer agent, generated by reaction of 1·2HI with Ag2O in the presence of a halide extractor, reactions with [Rh(COD)Cl]2 and [Rh(CO)2Cl]2 produced cationic dinuclear complexes bearing μ2-1 and μ2-Cl bridging ligands. The structural formulation of the novel dinuclear adducts of 1 was aided through spectroscopic congruence with model complexes, containing monodentate 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IiPr2Me2)

Synthesis and reactivity of NHC-based rhodium macrocycles

Using a general synthetic procedure employing readily accessed terminal alkene-functionalized pro-ligands and macrocyclization by ring-closing olefin metathesis, rhodium carbonyl complexes have been prepared that contain lutidine (1a; n = 1) and pyridine (1b; n = 0) derived tridentate CNC macrocycles with dodecamethylene spacers. In solution, 1a shows temperature-invariant time-averaged C2 symmetry by 1H NMR spectroscopy (CD2Cl2, 500 MHz), whereas in the solid-state, two polymorphs can be obtained showing different conformations of the alkyl spacer about the metal–carbonyl bond (asymmetric and symmetric). In contrast, time-averaged motion of alkyl spacer in 1b can be halted by cooling below 225 K (CD2Cl2, 500 MHz), and the complex crystallizes as a dimer with an interesting unsupported Rh···Rh bonding interaction (3.2758(6) Å). Oxidative addition reactions of 1a and 1b, using MeI and PhICl2, have been studied in situ by 1H NMR spectroscopy, although pure Rh(III) adducts can be ultimately isolated only with the pyridine-based macrocyclic ligand. The lutidine backbone of 1a can be deprotonated by addition of K[N(SiMe3)2], and the resulting neutral dearomatized complex (5) has been fully characterized in solution, by variable-temperature 1H NMR spectroscopy, and in the solid state, by X-ray diffraction

Asteroseismic surface gravity for evolved stars

Context: Asteroseismic surface gravity values can be of importance in determining spectroscopic stellar parameters. The independent log(g) value from asteroseismology can be used as a fixed value in the spectroscopic analysis to reduce uncertainties due to the fact that log(g) and effective temperature can not be determined independently from spectra. Since 2012, a combined analysis of seismically and spectroscopically derived stellar properties is ongoing for a large survey with SDSS/APOGEE and Kepler. Therefore, knowledge of any potential biases and uncertainties in asteroseismic log(g) values is now becoming important. Aims: The seismic parameter needed to derive log(g) is the frequency of maximum oscillation power (nu_max). Here, we investigate the influence of nu_max derived with different methods on the derived log(g) values. The large frequency separation between modes of the same degree and consecutive radial orders (Dnu) is often used as an additional constraint for the determination of log(g). Additionally, we checked the influence of small corrections applied to Dnu on the derived values of log(g). Methods We use methods extensively described in the literature to determine nu_max and Dnu together with seismic scaling relations and grid-based modeling to derive log(g). Results: We find that different approaches to derive oscillation parameters give results for log(g) with small, but different, biases for red-clump and red-giant-branch stars. These biases are well within the quoted uncertainties of ~0.01 dex (cgs). Corrections suggested in the literature to the Dnu scaling relation have no significant effect on log(g). However somewhat unexpectedly, method specific solar reference values induce biases of the order of the uncertainties, which is not the case when canonical solar reference values are used.Comment: 8 pages, 5 figures, accepted for publication by A&

Well-defined coinage metal transfer agents for the synthesis of NHC-based nickel, rhodium and palladium macrocycles

With a view to use as carbene transfer agents, well-defined silver(I) and copper(I) complexes of a macrocyclic NHC-based pincer ligand, bearing a central lutidine donor and a dodecamethylene spacer [CNC–(CH2)12, 1], have been prepared. Although the silver adduct is characterised by X-ray diffraction as a dinuclear species anti-[Ag(μ-1)]22+, variable temperature measurements indicate dynamic structural interchange in solution involving fragmentation into mononuclear [Ag(1)]+ on the NMR time scale. In contrast, a mononuclear structure is evident in both solution and the solid-state for the analogous copper adduct partnered with the weakly coordinating [BArF4]− counter anion. A related copper derivative, bearing instead the more coordinating cuprous bromide dianion [Cu2Br4]2−, is notable for the adoption of an interesting tetranuclear assembly in the solid-state, featuring two cuprophilic interactions and two bridging NHC donors, but is not retained on dissolution. Coinage metal precursors [M(1)]n[BArF4]n (M = Ag, n = 2; M = Cu, n = 1) both act as carbene transfer agents to afford palladium, rhodium and nickel complexes of 1 and the effectiveness of these precursors has been evaluated under equivalent reaction conditions

Rhodium(III) and iridium(III) complexes of a NHC-based macrocycle : persistent weak agostic interactions and reactions with dihydrogen

The synthesis and characterization of five-coordinate rhodium(III) and iridium(III) 2,2′-biphenyl complexes [M(CNC-12)(biph)][BArF4] (M = Rh (1a), Ir (1b)), featuring the macrocyclic lutidine- and NHC-based pincer ligand CNC-12 are reported. In the solid state these complexes are notable for the adoption of weak ε-agostic interactions that are characterized by M···H–C contacts of ca. 3.0 Å by X-ray crystallography and ν(CH) bands of reduced wavenumber by ATR IR spectroscopy. Remarkably, these interactions persist on dissolution and were observed at room temperature using NMR spectroscopy (CD2Cl2) and solution-phase IR spectroscopy (CCl4). The associated metrics point toward a stronger M···H–C interaction in the iridium congener, and this conclusion is borne out on interrogation of 1 in silico using DFT-based NBO and QTAIM analyses. Reaction of 1 with dihydrogen resulted in hydrogenolysis of the biaryl and formation of fluxional hydride complexes, whose ground state formulations as [Rh(CNC-12)H2][BArF4] (2a″) and [Ir(CNC-12)H2(H2)][BArF4] (2b‴) are proposed on the basis of inversion recovery and variable-temperature NMR experiments, alongside a computational analysis. Reactions of 1 and 2 with carbon monoxide help support their respective structural properties

Low-coordinate iridium NHC complexes derived from selective and reversible C–H bond activation of fluoroarenes

Interaction of the reactive 14 VE {Ir(IBioxMe4)3}+ fragment with fluoroarenes results exclusively in ortho-C–H bond oxidative addition and formation of 16 VE Ir(III) derivatives [Ir(IBioxMe4)3(Ar)H]+ (Ar = 2-C6H4F, 2,3-C6H3F2, 2,4,6-C6H2F3). The C–H bond activation reactions occur under mild conditions and are reversible

Solvent promoted reversible cyclometalation in a tethered NHC iridium complex

Reaction of [Ir(COD)(py–ItBu)]+ (py–ItBu = 3-tert-butyl-1-picolylimidazol-2-ylidene) with acetonitrile results in reversible intramolecular C–H bond activation of the NHC ligand and formation of [Ir(η2:η1-C8H13)(py–ItBu′)(NCMe)]+. Coordinated COD acts as an internal hydride acceptor and acetonitrile coordination offsets the otherwise unfavourable thermodynamics of the process

A convenient method for the generation of {Rh(PNP)}+ and {Rh(PONOP)}+ fragments : reversible formation of vinylidene derivatives

The substitution reactions of [Rh(COD)2][BArF4] with PNP and PONOP pincer ligands 2,6-bis(di-tert-butylphosphinomethyl)pyridine and 2,6-bis(di-tert-butylphosphinito)pyridine in the weakly coordinating solvent 1,2-F2C6H4 are shown to be an operationally simple method for the generation of reactive formally 14 VE rhodium(I) adducts in solution. Application of this methodology enables synthesis of known adducts of CO, N2, H2, previously unknown water complexes, and novel vinylidene derivatives [Rh(pincer)(CCHR)][BArF4] (R = tBu, 3,5-tBu2C6H3), through reversible reactions with terminal alkynes

The underlying physical meaning of the νmax−νc\nu_{\rm max}-\nu_{\rm c} relation

Asteroseismology of stars that exhibit solar-like oscillations are enjoying a growing interest with the wealth of observational results obtained with the CoRoT and Kepler missions. In this framework, scaling laws between asteroseismic quantities and stellar parameters are becoming essential tools to study a rich variety of stars. However, the physical underlying mechanisms of those scaling laws are still poorly known. Our objective is to provide a theoretical basis for the scaling between the frequency of the maximum in the power spectrum ($\nu_{\rm max}$) of solar-like oscillations and the cut-off frequency ($\nu_{\rm c}$). Using the SoHO GOLF observations together with theoretical considerations, we first confirm that the maximum of the height in oscillation power spectrum is determined by the so-called \emph{plateau} of the damping rates. The physical origin of the plateau can be traced to the destabilizing effect of the Lagrangian perturbation of entropy in the upper-most layers which becomes important when the modal period and the local thermal relaxation time-scale are comparable. Based on this analysis, we then find a linear relation between $\nu_{\rm max}$ and $\nu_{\rm c}$, with a coefficient that depends on the ratio of the Mach number of the exciting turbulence to the third power to the mixing-length parameter.Comment: 8 pages, 11 figures. Accepted in A&