How Solid Surfaces Control Stability and Interactions of Supported Cationic CuI(dppf) Complexes─A Solid-State NMR Study.

Organometallic complexes are frequently deposited on solid surfaces, but little is known about how the resulting complex-solid interactions alter their properties. Here, a series of complexes of the type Cu(dppf)(Lx)+ (dppf = 1,1'-bis(diphenylphosphino)ferrocene, Lx = mono- and bidentate ligands) were synthesized, physisorbed, ion-exchanged, or covalently immobilized on solid surfaces and investigated by 31P MAS NMR spectroscopy. Complexes adsorbed on silica interacted weakly and were stable, while adsorption on acidic γ-Al2O3 resulted in slow complex decomposition. Ion exchange into mesoporous Na-[Al]SBA-15 resulted in magnetic inequivalence of 31P nuclei verified by 31P-31P RFDR and 1H-31P FSLG HETCOR. DFT calculations verified that a MeCN ligand dissociates upon ion exchange. Covalent immobilization via organic linkers as well as ion exchange with bidentate ligands both lead to rigidly bound complexes that cause broad 31P CSA tensors. We thus demonstrate how the interactions between complexes and functional surfaces determine and alter the stability of complexes. The applied Cu(dppf)(Lx)+ complex family members are identified as suitable solid-state NMR probes for investigating the influence of support surfaces on deposited inorganic complexes.

Cooperativity-Driven Reactivity of a Dinuclear Copper Dimethylglyoxime Complex.

In this report, we present the dinuclear copper(II) dimethylglyoxime (H2 dmg) complex [Cu2 (H2 dmg)(Hdmg)(dmg)]+ (1), which, in contrast to its mononuclear analogue [Cu(Hdmg)2 ] (2), is subject to a cooperativity-driven hydrolysis. The combined Lewis acidity of both copper centers increases the electrophilicity of the carbon atom in the bridging µ2 -O-N=C-group of H2 dmg and thus, facilitates the nucleophilic attack of H2 O. This hydrolysis yields butane-2,3-dione monoxime (3) and NH2 OH that, depending on the solvent, is then either oxidized or reduced. In ethanol, NH2 OH is reduced to NH4 + , yielding acetaldehyde as the oxidation product. In contrast, in CH3 CN, NH2 OH is oxidized by CuII to form N2 O and [Cu(CH3 CN)4 ]+ . Herein are presented the combined synthetic, theoretical, spectroscopic and spectrometric methods that indicate and establish the reaction pathway of this solvent-dependent reaction.

Caging of a Strongly Pairing Fluorescent Thymidine Analog with Soft Nucleophiles.

Controlling the pairing strength of nucleobases in DNA through reactions with compounds found inside the cell is a formidable challenge. Here we report how a thiazolyl substituent turns a strongly pairing ethynylpyridone C-nucleoside into a reactive residue in oligonucleotides. The thiazolyl-bearing pyridone reacts with soft nucleophiles, such as glutathione, but not with hard nucleophiles like hydroxide or carbonate. The addition products pair much more weakly with adenine in a complementary strand than the starting material, and also change their fluorescence. This makes oligonucleotides containing the new deoxynucleoside interesting for controlled release. Due to its reactivity toward N, P, S, and Se-nucleophiles, and the visual signal accompanying chemical conversion, the fluorescent nucleotide reported here may also have applications in chemical biology, sensing and diagnostics.

Crystalline Anions Based on Classical N-Heterocyclic Carbenes.

Herein, the first stable anions K[SIPrBp ] (4 a-K) and K[IPrBp ] (4 b-K) (SIPrBp =BpC{N(Dipp)CH2 }2 , IPrBp =BpC{N(Dipp)CH}2 ; Bp=4-PhC6 H4 ; Dipp=2,6-iPr2 C6 H3 ) derived from classical N-heterocyclic carbenes (NHCs) (i.e. SIPr and IPr) have been isolated as violet crystalline solids. 4 a-K and 4 b-K are prepared by KC8 reduction of the neutral radicals [SIPrBp ] (3 a) and [IPrBp ] (3 b), respectively. The radicals 3 a and 3 b as well as [Me-IPrBp ] 3 c (Me-IPrBp =BpC{N(Dipp)CMe}2 ) are accessible as crystalline solids on treatment of the respective 1,3-imidazoli(ni)um bromides (SIPrBp )Br (2 a), (IPrBp )Br (2 b), and (Me-IPrBp )Br (2 c) with KC8 . The cyclic voltammograms of 2 a-2 c exhibit two one-electron reversible redox processes in -0.5 to -2.5 V region that correspond to the radicals 3 a-3 c and the anions (4 a-4 c)- . Computational calculations suggest a closed-shell singlet ground state for (4 a-4 c)- with the singlet-triplet energy gap of 17-24 kcal mol-1 .

Metal-metal communication between 1,1'-bis(diphenylphosphino)cobaltocenium and an organonickel moiety.

1,1'-Bis(diphenylphosphino)cobaltocenium (dppc)+, similar to 1,1'-bis(diphenylphosphino)ferrocene, can be coordinated by dicarbonylnickel(0) or cyclopentadienylnickel(II), respectively. The cyclic voltammogram of [Ni(CO)2(dppc)]+ ([1]+) showed two reversible reductions, at potentails nearly identical to (dppc)+. The ligand-based reductions were confirmed by IR spectroelectrochemistry (SEC), although the ΔνCO was larger than might be expected if the ligand was electronically decoupled to the Ni(CO)2 moiety. The larger ΔνCO was attibuted to changes in the donor/accpetor properties of the -PPh2 moeities based on the occupation of the Co-Cp anti-bonding orbital, where the Cp ligand adopts an ylide-like structure. A similar analysis was performed on [CpNi(dppc)]2+ ([2]2+), where the two reductions were anodically shifted by ΔE = 292 and 520 mV from (dppc)+, indicating an increase in the M-M communication. The EPR SEC spectrum for [2]+ showed that the cobalt was reduced, while the UV-Vis-NIR SEC spectrum for [2]+ showed a NIR absportion at 1200 nm assinged as a MMCT CoII → NiII band. The second reduction formed [2]0 which was EPR silent but the UV-Vis-NIR SEC spectrum showed an increase in the intensity of the MMCT CoI → NiII.

Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates.

We report the synthesis and the reactivity of 1,2,3-triazolin-5-imine type mesoionic imines (MIIs). The MIIs are accessible by a base-mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O-stretching frequencies in MII-CO2 and -Rh(CO)2 Cl complexes were used to determine the overall donor strength. The MIIs are stronger donors than the N-heterocyclic imines (NHIs). MIIs are excellent ligands for main group elements and transition metals in which they display substituent-induced fluorine-specific interactions and undergo C-H activation. DFT calculations gave insights into the frontier orbitals of the MIIs. The calculations predict a relatively small HOMO-LUMO gap compared to other related ligands. MIIs are potentially able to act as both π-donor and π-acceptor ligands. This report highlights the potential of MIIs to display exciting properties with a huge potential for future development.

Synthesis and Characterization of Bidentate Isonitrile Iron Complexes.

The divalent iron complexes trans-[FeBr2(BINC)2], [Cp*FeCl(BINC)] (Cp* = Me5C5), and [FeBr2(CNAr3NC)2] with the chelating bis(isonitrile) ligands BINC (bis(2-isocyanophenyl)phenylphosphonate) and CNAr3NC (2,2″-diisocyano-3,5,3″,5"tetramethyl-1,1':3',1″-terphenyl) have been prepared and characterized. Their subsequent reduction yields the di- and trinuclear compounds [Fe3(BINC)6], [Cp*Fe(BINC)]2, [Fe(CNAr3NC)2]2, and [K(Et2O)]2[Fe(CNAr3NC)2]2. The molecular structures of all new species were determined by X-ray crystallography and compared to those of related iron carbonyl complexes, demonstrating that the bidentate isonitrile ligands are capable surrogates for two CO ligands with only minimal distortion of the tetrahedral or octahedral geometry of the parent complexes. The complexes were further characterized by NMR and IR spectroscopy, and the electrochemical properties of selected compounds were analyzed by UV-vis-NIR spectroelectrochemistry.

[(η6-p-Cymene)[3-(pyrid-2-yl)-1,2,4,5-tetrazine]chlororuthenium(II)]+, Redox Noninnocence and Dienophile Addition to Coordinated Tetrazine.

The bidentate ligand 3-(pyrid-2-yl)-1,2,4,5-tetrazine (TzPy) coordinated in the complex [CyRuCl(TzPy)]PF6 ([1]+; Cy = η6-p-cymene) shows noninnocent behavior and can be modified through the addition of dienophiles, vinylferrocene (ViFc) or ethynylferrocene (EthFc). The kinetics and transition-state thermodynamic analysis of the reaction of [1]+ + ViFc found ΔG⧧(298 K) = 67 kJ mol-1, while that of [1]+ + EthFc was ΔG⧧(298 K) = 83 kJ mol-1. The room temperature second-order rate of [1]+ + EthFc, k2 = 1.51(4) × 10-2 M-1 s-1, was 3 orders of magnitude faster than that of EthFc + TzPy, k2 = 1.05(15) × 10-4 M-1 s-1. The [1H2Fc]+ complex was converted to [1Fc]+ by oxidation with oxygen and 3,5-di-tert-butyl-o-quinone, and the molecular structure of [1Fc]+ was determined by single-crystal X-ray diffraction. The title complex [1]+ showed a quasi-reversible reduction in the cyclic voltammogram, and the electrochemical reduction mechanism was determined by UV-vis spectroelectrochemistry (SEC) experiments, as well as supported by density functional theory (DFT) calculations. The dihydropyridazine [1H2Fc]+ and pyridazine [1Fc]+ states of the ligand showed ligand noninnocence similar to that of the parent tetrazine but at a cathodically shifted potential. The dihydropyridazine [1H2Fc]+ showed a mixture of several products; however, upon oxidation, only a single product, [1Fc]+, was formed from the endo addition of the dienophile to [1]+. The electrochemical mechanism of [1Fc]+ was also studied by cyclic voltammetry and UV-vis SEC experiments, as well as supported by DFT calculations.

Electronic Structure of a Diiron Complex: A Multitechnique Experimental Study of [(dppf)Fe(CO) 3]+/0.

Here we explore the electronic structure of the diiron complex [(dppf)Fe(CO)3]0/+ [10/+; dppf = 1,1'-bis(diphenylphosphino)ferrocene] in two oxidation states by an advanced multitechnique experimental approach. A combination of magnetic circular dichroism, X-ray absorption and emission, high-frequency electron paramagnetic resonance (EPR), and Mössbauer spectroscopies is used to establish that oxidation of 10 occurs on the carbonyl iron ion, resulting in a low-spin iron(I) ion. It is shown that an unequivocal result is obtained by combining several methods. Compound 1+ displays slow spin dynamics, which is used here to study its geometric structure by means of pulsed EPR methods. Surprisingly, these data show an association of the tetrakis[3,5-bis(trifluoromethylphenyl)]borate counterion with 1+.

The core of the matter - arene substitution determines the coordination and catalytic behaviour of tris(1-phosphanyl-1'-ferrocenylene)arene gold(I) complexes.

Changing the aromatic core of C3-symmetric tris(ferrocenyl)arene-based tris-phosphanes has profound effects on their coordination behaviour towards gold(i). Depending on the arene (s-triazine, benzene, or trifluorobenzene), four different coordination modes can be distinguished and their preference has been rationalised using computational methods. The corresponding 1 : 1 ligand-to-metal complexes, studied by variable-temperature NMR spectroscopy, revealed fluctional behaviour in solution. Given the presence of up to three or six ferrocenylene spacers per complex, their electrochemistry was investigated. The redox-responsive nature of the complexes can be advantageously exploited in the catalytic ring-closing isomerisation of N-(2-propyn-1-yl)benzamide, where the benzene-based 2 : 3 ligand-to-metal complex has been shown to display multiple activity states depending on the degree of (reversible) oxidation in a preliminary trial.

Tetrazine metallation boosts rate and regioselectivity of inverse electron demand Diels-Alder (iEDDA) addition of dienophiles.

Reported herein is the coordination of rhenium complexes to tetrazine ligand in [ReCl(CO)3(TzPy)] [1] (TzPy = 3-(2-pyridyl)-1,2,4,5-tetrazine) and the rates of addition of different dienophiles to the tetrazine. Tetrazine coordiation lowers the ΔS‡ contribution to ΔG‡ for iEDDA addition.

Influence of Multisite Metal-Ligand Cooperativity on the Redox Activity of Noninnocent N2S2 Ligands.

Metal-ligand cooperativity (MLC) relies on chemically reactive ligands to assist metals with small-molecule binding and activation, and it has facilitated unprecedented examples of catalysis with metal complexes. Despite growing interest in combining ligand-centered chemical and redox reactions for chemical transformations, there are few studies demonstrating how chemically engaging redox active ligands in MLC affects their electrochemical properties when bound to metals. Here we report stepwise changes in the redox activity of model Ru complexes as zero, one, and two BH3 molecules undergo MLC binding with a triaryl noninnocent N2S2 ligand derived from o-phenylenediamine (L1). A similar series of Ru complexes with a diaryl N2S2 ligand with ethylene substituted in place of phenylene (L2) is also described to evaluate the influence of the o-phenylenediamine subunit on redox activity and MLC. Cyclic voltammetry (CV) studies and density functional theory (DFT) calculations show that MLC attenuates ligand-centered redox activity in both series of complexes, but electron transfer is still achieved when only one of the two redox-active sites on the ligands is chemically engaged. The results demonstrate how incorporating more than one multifunctional reactive site could be an effective strategy for maintaining redox noninnocence in ligands that are also chemically reactive and competent for MLC.

Tricoordinate Coinage Metal Complexes with a Redox-Active Tris-(Ferrocenyl)triazine Backbone Feature Triazine-Metal Interactions.

Invited for the cover of this issue is the group of Evamarie Hey-Hawkins at the University of Leipzig and colleagues at the University of Stuttgart and University of Regensburg. The image depicts the reported complexes as three similar flowers growing from one common branch representing the ligand. Read the full text of the article at 10.1002/chem.202000226.

Tricoordinate Coinage Metal Complexes with a Redox-Active Tris-(Ferrocenyl)triazine Backbone Feature Triazine-Metal Interactions.

2,4,6-Tris(1-diphenylphosphanyl-1'-ferrocenylene)-1,3,5-triazine (1) coordinates all three coinage metal(I) ions in a 1:1 tridentate coordination mode. The C3 -symmetric coordination in both solid state and solution is stabilised by an uncommon cation-π interaction between the triazine core and the metal cation. Intramolecular dynamic behaviour was observed by variable-temperature NMR spectroscopy. The borane adduct of 1, 1BH3 , displays four accessible oxidation states, suggesting complexes of 1 to be intriguing candidates for redox-switchable catalysis. Complexes 1Cu, 1Ag, and 1Au display a more complicated electrochemical behaviour, and the electrochemical mechanism was studied by temperature-resolved UV/Vis spectroelectrochemistry and chemical oxidation.

Redox-inactive ions control the redox-activity of molecular vanadium oxides.

Polyoxometalates are key materials for energy conversion and storage due to their unique chemical tunability and electrochemical reactivity. Herein, we report that functionalization of molecular vanadium oxides, polyoxovanadates, with redox-inert Ca2+ cations leads to a significant increase in their electron storage capabilities. The electrochemical performance of the Ca2+-functionalized dodecavanadate [Ca2V12O32Cl(DMF)3]2- (={Ca 2 V 12 }) was thus compared with that of the precursor compound (H2NMe2)2[V12O32Cl]3- (={V 12 }). {Ca 2 V 12 } can store up to five electrons per cluster, while {V 12 } only shows one reversible redox transition. In initial studies, we demonstrated that {Ca 2 V 12 } can be used as an active material in lithium-ion cathodes. Our results show how redox-inert cations can be used as structural and electrostatic stabilizers, leading to major changes in the redox-chemistry of polyoxovanadates.

(Benz-)imidazolin-2-ylidene-benzimidazolatonickel(II) Chelates: Syntheses, Structures, and Tuning of Noninnocent Chelate Ligand Behavior.

The deprotonation of 1-(1H-benzimidazol-2-yl)-3-methylbenzimidazolium hexafluorophosphate (2MeH2[PF6]) and 1-(1H-benzimidazol-2-yl)-3-isopropylbenzimidazolium hexafluorophosphate (2iPrH2[PF6]) with potassium tert-butoxide in THF afforded the benzimidazolium-benzimidazolates 2MeH and 2iPrH. The "instant carbene" behavior of these conjugated mesomeric betaines was demonstrated by trapping their carbenic tautomers 2'MeH and 2'iPrH with elemental sulfur and selenium, which afforded the corresponding thio- and selenourea derivatives 2'MeHE and 2'iPrHE (E = S, Se). The treatment of 2MeH and 2iPrH with nickelocene furnished the nickel(II) complexes [NiCp(2'Me)] and [NiCp(2'iPr)], which contain an anionic C,Namido-chelating NHC ligand. The electronic structure and redox behavior of the nickel(II) chelates were investigated, as well as those of the closely related chelates [NiCp(1'Me)] and [NiCp(1'iPr)] derived from the corresponding imidazolium-benzimidazolates 1MeH and 1iPrH. According to DFT calculations, the highest occupied molecular orbital (HOMO) is located over the NiCp moiety and the π system of the chelate ligand with a large contribution from the (benz-)imidazolate moiety. Cyclic voltammetry revealed a reversible oxidation to the monocation [NiCp(L)]+ (E1/2 = 0.315, 0.222, 0.396, 0.265 V vs ferrocene/ferrocenium for L = 1'Me, 1'iPr, 2'Me, 2'iPr, respectively) in CH2Cl2/0.1 M n-Bu4N[B(ArF)4] (B(ArF)4- = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), and isosbestic behavior was found in UV-vis-NIR spectroelectrochemical experiments. The different redox potentials reflect the different donor/acceptor properties of the NHC part of the chelate ligands, with 1'iPr being the strongest and 2'Me the weakest net electron donor. The EPR spectroscopic signature of [NiCp(2'Me)]+ in CH2Cl2/0.1 M n-Bu4N[B(ArF)4] at 100 K is consistent with a chelate-ligand-based radical with strong spin-orbit coupling to the Ni center. In contrast, the EPR spectra of [NiCp(1'Me)]+, [NiCp(1'iPr)]+, and [NiCp(2'iPr)]+ indicate that these monocations are best described as NiIII complexes, the comparatively higher contribution of the NiIII(L) vs the NiII(L•+) valence tautomer being supported by the results of open-shell DFT calculations.

Reply to Comment on Stabilization of Low-Valent Iron(I) in a High-Valent Vanadium(V) Oxide Cluster.

The authors of the Communication "Stabilization of Low-Valent Iron(I) in a High-Valent Vanadium(V) Oxide Cluster" reply to a Comment by Dr. Sproules, who offered an alternative interpretation of the metal oxidation states in the two electron reduced iron vanadate (NH2 Me2 )[(FeCl)V12 O32 Cl]4- .

Polyfunctional Imidazolium Aryloxide Betaine/Lewis Acid Catalysts as Tools for the Asymmetric Synthesis of Disfavored Diastereomers.

Enzymes are Nature's polyfunctional catalysts tailor-made for specific biochemical synthetic transformations, which often proceed with almost perfect stereocontrol. From a synthetic point of view, artificial catalysts usually offer the advantage of much broader substrate scopes, but stereocontrol is often inferior to that possible with natural enzymes. A particularly difficult synthetic task in asymmetric catalysis is to overwrite a pronounced preference for the formation of an inherently favored diastereomer; this requires a high level of stereocontrol. In this Article, the development of a novel artificial polyfunctional catalyst type is described, in which an imidazolium-aryloxide betaine moiety cooperates with a Lewis acidic metal center (here Cu(II)) within a chiral catalyst framework. This strategy permits for the first time a general, highly enantioselective access to the otherwise rare diastereomer in the direct 1,4-addition of various 1,3-dicarbonyl substrates to ß-substituted nitroolefins. The unique stereocontrol by the polyfunctional catalyst system is also demonstrated with the highly stereoselective formation of a third contiguous stereocenter making use of a diastereoselective nitronate protonation employing α,ß-disubstituted nitroolefin substrates. Asymmetric 1,4-additions of ß-ketoesters to α,ß-disubstituted nitroolefins have never been reported before in literature. Combined mechanistic investigations including detailed spectroscopic and density functional theory (DFT) studies suggest that the aryloxide acts as a base to form a Cu(II)-bound enolate, whereas the nitroolefin is activated by H-bonds to the imidazolium unit and the phenolic OH generated during the proton transfer. Detailed kinetic analyses (RPKA, VTNA) suggest that (a) the catalyst is stable during the catalytic reaction, (b) not inhibited by product and (c) the rate-limiting step is most likely the C-C bond formation in agreement with the DFT calculations of the catalytic cycle. The robust catalyst is readily synthesized and recyclable and could also be applied to a cascade cyclization.