Radical Complex Research Articles

Malignant sarcomatous transformation of calvarial fibrous dysplasia: illustrative case.

Fibrous dysplasia (FD) is a nonheritable genetic disorder characterized by abnormal osteogenesis, resulting in benign bone lesions in one or multiple bones. Despite their predominantly benign nature, these lesions can transform into malignant neoplasms, resulting in pain, swelling, disfigurement, and even death. The authors report a case of malignant sarcomatous transformation in an adult patient with a history of craniofacial FD. A 61-year-old male with a history of systemic FD presented with a rapidly enlarging cranial mass that had recently started becoming painful to touch. Magnetic resonance imaging of the brain displayed extensive FD changes throughout the calvarium and a large dysplastic mass in the right parietal bone with extension into the underlying epidural space, resulting in severe mass effect. The patient subsequently underwent radical resection and complex soft tissue reconstruction. The pathology confirmed high-grade undifferentiated pleomorphic sarcoma, for which the patient subsequently underwent an adjuvant chemotherapy regimen. Malignant sarcomatous transformation of craniofacial FD most often results in the formation of an osteosarcoma in the maxilla, with the temporal and sphenoid bones also being common sites of such transformations. Although treatment begins with radical resection, the efficacy of adjuvant chemotherapy and radiation remains controversial. https://thejns.org/doi/10.3171/CASE24537.

Strong Antiferromagnetic Interactions in the Binuclear Cobalt(II) Complex with a Bridged Nitroxide Diradical

A binuclear cobalt–radical complex formed by the reaction of Co(hfac)2·2H2O (hfac = hexafluoroacetylacetonate) with the 2,2-bis(1-oxyl-3-oxide-4,4,5,5-tetramethylimidazolinyl) biradical (BR) has been synthesized. The complex {(hfac)CoII(BN)CoII(hfac)} crystallizes in the triclinic space group P1¯ : C34H28Co2F24N4O12, a = 11.1513(5) Å, b = 12.8362(7) Å, c = 18.2903(8) Å, α = 103.061(1)°, β = 100.898(2)°, γ = 102.250(1)°, Z = 2. The compound consists of two non-equivalent pseudo-octahedral CoII ions, each bearing two hfac ancillary ligands bridged by the tetradentate bis-nitroxide (BN). The temperature dependence of the magnetic susceptibility indicates a strong antiferromagnetic exchange between each of the Co2+ ions and the nitroxyl biradical, as well as between the spins within the bridging ligand, forming a spin-frustrated system. Micro-squid investigations, performed on a single crystal of {(hfac)CoII(BN)CoII(hfac)}, reveal a peculiarity of the M(H) graph at temperatures below 0.4 K displaying a step that is a result of ground and first excited levels mixing by the applied magnetic field due to a small energy gap between them, as inferred from ab initio calculation. The latter was also carried out for two models of mononuclear Co2+ complexes in order to obtain a set of initial parameters for fitting the experimental magnetic curves using the Phi program. Moreover, direct CAS(12,10)/def2-TZVP calculations of the magnetic dependences χT(T) and M(H) were performed, which satisfactorily reproduced the experimental ones.

A Structural and Functional Mimic of P680+

One or multiple chlorophyll molecules are employed in the reaction center of photosystem II's main electron donor (defined as P680). We have a poor understanding of how the reaction center facilitates water oxidation and the roles that mono‐ and/or multimeric chlorophyll groups play when P680 oxidizes a neighboring tyrosine in order to drive water oxidation at the oxygen evolving complex. We have prepared a dimeric MgII‐porphyrin complex [Mg2(BTPP)] (1, H4‐BTPP = 1,2‐bis‐(10,15,20‐triphenylporphyrin‐5‐yl)‐benzene) as a structural and functional mimic of the dimeric core of P680. 1 was oxidized by one‐electron to the corresponding π‐cation radical complex 2. The radical cation was characterized by UV‐Vis‐NIR, FT‐IR, and EPR spectroscopic techniques. 2 was shown to be reactive towards phenols to give the corresponding phenoxyl radicals, mimicking the reactivity of the P680 cation radical which oxidizes tyrosine to tyrosyl radical. Critically, the dimeric π‐cation radical showed markedly higher rates of proton coupled electron transfer oxidation (PCET) of phenols when compared to its monomeric counterpart [Mg(TPP)] (TPP = 5,10,15,20‐tetraphenylporphyrin). Our findings demonstrate that MgII‐porphyrin complexes are reliable mimics of photosynthetic PCET processes and suggest that photosynthetic reaction centers with multiple π‐conjugated complexes likely lower the barrier to PCET oxidation by π‐cation radical species.

A Structural and Functional Mimic of P680.

One or multiple chlorophyll molecules are employed in the reaction center of photosystem II's main electron donor (defined as P680). We have a poor understanding of how the reaction center facilitates water oxidation and the roles that mono- and/or multimeric chlorophyll groups play when P680 oxidizes a neighboring tyrosine in order to drive water oxidation at the oxygen evolving complex. We have prepared a dimeric MgII-porphyrin complex [Mg2(BTPP)] (1, H4-BTPP = 1,2-bis-(10,15,20-triphenylporphyrin-5-yl)-benzene) as a structural and functional mimic of the dimeric core of P680. 1 was oxidized by one-electron to the corresponding π-cation radical complex 2. The radical cation was characterized by UV-Vis-NIR, FT-IR, and EPR spectroscopic techniques. 2 was shown to be reactive towards phenols to give the corresponding phenoxyl radicals, mimicking the reactivity of the P680 cation radical which oxidizes tyrosine to tyrosyl radical. Critically, the dimeric π-cation radical showed markedly higher rates of proton coupled electron transfer oxidation (PCET) of phenols when compared to its monomeric counterpart [Mg(TPP)] (TPP = 5,10,15,20-tetraphenylporphyrin). Our findings demonstrate that MgII-porphyrin complexes are reliable mimics of photosynthetic PCET processes and suggest that photosynthetic reaction centers with multiple π-conjugated complexes likely lower the barrier to PCET oxidation by π-cation radical species.

Reactivity of Strontium Hydride Supported by the Superbulky Hydrotris(pyrazolyl)borate Ligand.

Hydrogenolysis of [(TpAd,iPr)Sr{CH(SiMe3)2}] (1) (TpAd,iPr = hydrotris(3-adamantyl-5-isopropyl-pyrazolyl)borate) in hexane solution under 20 atm of H2 allowed for the isolation of strontium hydride [(TpAd,iPr)Sr(μ-H)]2 (2) in good yield. Complex 2 exhibits the dimeric nature in solid state, featuring two different bond modes between the Sr center and TpAd,iPr ligand. Treatment of complex 2 with PhC(H)═NtBu or PhCH2Bpin (Bpin = pinacolateborane) afforded the strontium amide complex [(TpAd,iPr)Sr{N(CH2Ph)(tBu)}] (4) and hydroborate complex [(TpAd,iPr)Sr{μ-HBpin(CH2Ph)}] (5), respectively. Reactions of complex 2 with 2-picoline, 2-phenylquinoline, or 2-phenylpyridine led to the formation of strontium 2-pyridylmethylene/2-picoline complex [(TpAd,iPr)Sr(2-CH2-Py)(2-picoline)] (6), reductively coupling diphenyl-biquinolide complex [{(TpAd,iPr)Sr}2(2,2'-Ph2-4,4'-dihydro-4,4'-biquinolide)] (7), and diphenyl-bipyridyl radical complex [(TpAd,iPr)Sr(6,6'-Ph2-2,2'-bipyridyl)] (8), separately. All of the complexes have been well characterized, including NMR spectrum and single-crystal X-ray analysis.

Isolation of Elusive Fluoflavine Radicals in Two Differing Oxidation States.

Facile access and switchability between multiple oxidation states are key properties of many catalytic applications and spintronic devices yet poorly understood due to inherent complications arising from isolating a redox system in multiple oxidation states without drastic structural changes. Here, we present the first isolable, free fluoflavine (flv) radical flv(1-•) as a bottleable potassium compound, [K(crypt-222)](flv•), 1, and a new series of organometallic rare earth complexes [(Cp*2Y)2(μ-flvz)]X, (where Cp* = pentamethylcyclopentadienyl, X = [Al(OC{CF3}3)4]- (z = -1), 2; X = 0 (z = -2), 3; [K(crypt-222)]+ (z = -3), 4) comprising the flv ligand in three different oxidation states, two of which are paramagnetic flv1-• and flv3-•. Excitingly, 1, 2, and 4 constitute the first isolable flv1-• and flv3-• radical complexes and, to date, the only isolated flv radicals of any oxidation state. All compounds are accessible in good crystalline yields and were unambiguously characterized via single-crystal X-ray diffraction analysis, cyclic voltammetry, IR-, UV-vis, and variable-temperature EPR spectroscopy. Remarkably, the EPR spectra for 1, 2, and 4 are distinct and a testament to stronger spin delocalization onto the metal centers as a function of higher charge on the flv radical. In-depth analysis of the electron- and spin density via density functional theory (DFT) calculations utilizing NLMO, QTAIM, and spin density topology analysis confirmed the fundamental interplay of metal coordination, ligand oxidation state, aromaticity, covalency, and spin density transfer, which may serve as blueprints for the development of future spintronic devices, single-molecule magnets, and quantum information science at large.

Lie algebras arising from two-periodic projective complex and derived categories

Let A be a finite-dimensional C-algebra of finite global dimension and A be the category of finitely generated right A-modules. By using of the category of two-periodic projective complexes C2(P), we construct the motivic Bridgeland's Hall algebra for A, where structure constants are given by Poincaré polynomials in t, then construct a C-Lie subalgebra g=n⊕h at t=−1, where n is constructed by stack functions about indecomposable radical complexes, and h is by contractible complexes. For the stable category K2(P) of C2(P), we construct its moduli spaces and a C-Lie algebra g˜=n˜⊕h˜, where n˜ is constructed by support-indecomposable constructible functions, and h˜ is by the Grothendieck group of K2(P). We prove that the natural functor C2(P)→K2(P) together with the natural isomorphism between Grothendieck groups of A and K2(P) induces a Lie algebra isomorphism g≅g˜. This makes clear that the structure constants at t=−1 provided by Bridgeland in [5] in terms of exact structure of C2(P) precisely equal to that given in [30] in terms of triangulated category structure of K2(P).

From d8 to d1: Iron(0) and Iron(I) Complexes Complete the Series of Eight Fe Oxidation States within the TIMMNMes Ligand Framework.

Reduction of the ferrous precursor [(TIMMNMes)Fe(Cl)]+ (1) (TIMMNMes = tris-[(3-mesitylimidazol-2-ylidene)methyl]amine) to the low-valent iron(0) complex [(TIMMNMes)Fe(CO)3] (2) is presented, where the tris(N-heterocyclic carbene) (NHC) ligand framework remains intact, yet the coordination mode changed from 3-fold to 2-fold coordination of the carbene arms. Further, the corresponding iron(I) complexes [(TIMMNMes)Fe(L)]+ (L = free site, η1-N2, CO, py) (3) are synthesized and fully characterized. Complexes 1-3 demonstrate the notable steric and electronic flexibility of the TIMMNMes ligand framework by variation of the Fe-N anchor and Fe-carbene distances and the variable size of the axial cavity occupation. This is further underpinned by the oxidation of 3-N2 in a reaction with benzophenone to yield the corresponding, charge-separated iron(II) radical complex [(TIMMNMes)Fe(OCPh2)]+ (4). We found rather surprising similarities in the reactivity behavior when going to low- or high-valent oxidation states of the central iron ion. This is demonstrated by the closely related reactivity of 3-N2, where H atom abstraction with TEMPO triggers the formation of the metallacycle [(TIMMNMes*)Fe(py)]+ (5), and the reactivity of the highly unstable Fe(VII) nitride complex [(TIMMNMes)Fe(N)(F)]3+ to give the metallacyclic Fe(V) imido complex [(TIMMNMesN)Fe(NMes)(MeCN)]3+ (6) upon warming. Thus, the employed tris(carbene) chelate is not only capable of stabilizing the superoxidized Fe(VI) and Fe(VII) nitrides but equally supports the iron center in its low oxidation states 0 and +1. Isolation and characterization of these zero- and monovalent iron complexes demonstrate the extraordinary capability of the tris(carbene) chelate TIMMN to support iron in eight different oxidation states within the very same ligand platform.

Stepwise Photochromism of Large Macrocycles Incorporating Two Negative Photochromic Units.

Macrocyclic photochromic molecules incorporating multiple photochromic units are known to exhibit cooperative and nonlinear photochromic reactions among distinct photochromic components. While extensive research has concentrated on positive photochromic molecules, this study presents a pioneering attempt in synthesizing macrocyclic photochromic molecules that integrate negative photochromic units. Binaphthyl-bridged phenoxyl imidazolyl radical complex, BN-PIC, exhibits unique negative photochromism in which the thermally stable colored isomer converts to the metastable colorless isomer via a short-lived biradical upon visible-light irradiation. Macrocyclic biphotochromic molecules incorporating two BN-PIC units were synthesized and the effects of ring strain on the photochromic properties including the photoconversion efficiencies and the rates of the thermal reverse reaction were investigated. The photokinetic study of these macrocyclic biphotochromic molecules demonstrated that the structural distortion of the ring caused by the isomerization of one photochromic unit significantly influenced the photoisomerization efficiency and the rate of the thermal reverse reaction of the other photochromic unit.

Synthesis and Reactivity of the Rare-Earth Metal Complexes Bearing the Indol-2-yl-Based NCN Pincer Ligand.

The pincer rare-earth dialkyl complexes [κ3-LRE(CH2SiMe3)2 (RE = Lu(1a), Yb(1b), Er(1c), Y(1d), Dy(1e))] with the indol-2-yl-based NCN pincer ligand were synthesized by the reactions of the proligand HL (L = 1-Me2NCH2CH2-3-(2-iPrC6H5N═CH)C8H4N) with RE(CH2SiMe3)3(THF)2. These complexes exhibited a variety of reactivities toward organic compounds such as amines, triphenylphosphine ylide, N-phenylimidazole, pyridine derivatives, and o-carborane leading to σ-bond metathesis, migration insertion, and redox reaction products. The reactions of the dialkyl rare-earth metal complexes with o-carborane afforded the novel NCN pincer-ligated carboryne-based metallacyclopropanes which reacted with diphenyl ketone to give insertion products of the RE-C2-ind and one of the RE-Ccage bonds, while the reaction of the carboryne-based metallacyclopropanes with diphenyldiazomethane produced the di-aza-metallacyclopentanes via the insertions of the N═N bond of the diphenyldiazomethane into two RE-Ccage bonds and the RE-C2-ind bond. The reactions of the dialkyl complexes with 2 equiv of 2,2'-bipyridine afforded the pincer-ligated bis(2,2'-bipyridyl monoanionic radical) complexes via the homolytic redox reaction.

A Mechanistic Study on Iron-Based Styrene Aziridination: Understanding Epoxidation via Nitrene Hydrolysis.

Transition-metal-catalyzed nitrene transfer reactions are typically performed in organic solvents under inert and anhydrous conditions due to the involved air and water-sensitive nature of reactive intermediates. Overall, this study provides insights into the iron-based ([FeII(PBI)3](CF3SO3)2 (1), where PBI = 2-(2-pyridyl)benzimidazole), catalytic and stoichiometric aziridination of styrenes using PhINTs ([(N-tosylimino)iodo]benzene), highlighting the importance of reaction conditions including the effects of the solvent, co-ligands (para-substituted pyridines), and substrate substituents on the product yields, selectivity, and reaction kinetics. The aziridination reactions with 1/PhINTs showed higher conversion than epoxidation with 1/PhIO (iodosobenzene). However, the reaction with PhINTs was less selective and yielded more products, including styrene oxide, benzaldehyde, and 2-phenyl-1-tosylaziridine. Therefore, the main aim of this study was to investigate the potential role of water in the formation of oxygen-containing by-products during radical-type nitrene transfer catalysis. During the catalytic tests, a lower yield was obtained in a protic solvent (trifluoroethanol) than in acetonitrile. In the case of the catalytic oxidation of para-substituted styrenes containing electron-donating groups, higher yield, TON, and TOF were achieved than those with electron-withdrawing groups. Pseudo-first-order kinetics were observed for the stoichiometric oxidation, and the second-order rate constants (k2 = 7.16 × 10-3 M-1 s-1 in MeCN, 2.58 × 10-3 M-1 s-1 in CF3CH2OH) of the reaction were determined. The linear free energy relationships between the relative reaction rates (logkrel) and the total substituent effect (TE, 4R-PhCHCH2) parameters with slopes of 1.48 (MeCN) and 1.89 (CF3CH2OH) suggest that the stoichiometric aziridination of styrenes can be described through the formation of a radical intermediate in the rate-determining step. Styrene oxide formation during aqueous styrene aziridination most likely results from oxygen atom transfer via in situ iron oxo/oxyl radical complexes, which are formed through the hydrolysis of [FeIII(N•Ts)] under experimental conditions.

Dichloromethane as C1 Synthon for the Photoredox Catalytic Cyclopropanation of Aromatic Olefins

AbstractDichloromethane, as a readily available and inexpensive C1 synthon is proposed as a powerful building block for cyclopropanation of alkenes under mild conditions. Herein, we report a highly efficient and versatile dual photoredox system, involving a nickel aminopyridine coordination complex and a photocatalyst, for the cyclopropanation of aromatic olefins using dichloromethane, under visible‐light irradiation. The cyclopropanation protocol has been successfully applied at gram scale. Mechanistic studies suggest a Ni(II) pyridyl radical complex as the key intermediate for the homolytic cleavage of the Csp3−Cl bond, generating a chloromethyl radical that is captured by the olefin coupling partner. Our findings also highlight the versatility of this methodology. By directing the radical/polar crossover process, we were able to selectively drive the reaction towards either the formation of cyclopropyl derivatives or the corresponding non‐cyclic alkyl chloride products. The methodology also successfully apply to geminal dichloroalkanes, including the formation of spiro[2,2] compounds. Moreover, our methodology extends to the synthesis of deuterium‐labelled cyclopropanes, demonstrating its utility in isotopic labelling and broadening its applicability in chemical synthesis and drug development.

Synthesis and Characterization of Bridging-Diazene Diiron Half-Sandwich Complexes: The Role of Sulfur Hydrogen Bonding.

We report two bridging-diazene diiron complexes [Cp*Fe(8-quinolinethiolate)]2(μ-N2H2) (1-N2H2) and [Cp*Fe(1,2-Cy2PC6H4S)]2(μ-N2H2) (2-N2H2), synthesized by the reaction of hydrazine with the corresponding thiolate-based iron half-sandwich complex, [Cp*Fe(8-quinolinethiolate)]2 (1) and Cp*Fe(1,2-Cy2PC6H4S) (2). Crystallographic analysis reveals that the thiolate sites in 1-N2H2 and 2-N2H2 can engage in N-H···S hydrogen bonding with the diazene protons. 1-N2H2 is thermally stable in both solid and solution states, allowing for one-electron oxidation to afford a cationic diazene radical complex [1-N2H2]+ at room temperature. In contrast, 2-N2H2 tends to undergo N2H2/N2 transformation, leading to the formation of a Fe(III)-H species by the loss of N2. In addition to stabilizing HN=NH species through the hydrogen bonding, the thiolate-based ligands also seem to facilitate proton-coupled electron transfer, thereby promoting N-H cleavage.

Robust free-base and metalated corrole radicals with reduction-induced emission

Preparing free-base porphyrinoid radicals that can function as coordination ligands is a challenging task. Here we report the synthesis of a stable, free-base benzocorrole (BC) radical containing only two inner NH protons via a retro-Diels-Alder conversion. The radical character of BC was fully supported by crystallographic analysis, spectroscopic evidence, and theoretical calculations. This neutral radical ligand allowed easy insertion of Zn(II), Ga(III), and Pd(II) ions to produce radical complexes. All these radicals exhibited luminescence-on responses under weak reducing atmosphere, corresponding to the conversion to their aromatic anions. The red fluorescence was observed for BC and its Zn(II) and Ga(III) complexes, and the near-infrared phosphorescence (> 900 nm) was detected for Pd(II) complex at room temperature. Furthermore, Ga(III) corrole exhibited a variation in fluorescence in response to axial coordination. Our findings provide a promising radical platform for coordination and developing novel functional materials with switchable spin and emission.

Monomethylation and -protonation of Lutetium Dinitrogen Complex.

Due to the highly chemically inert nature, direct activation and transformation of dinitrogen are challenging. Here, we disclose the synthesis, isolation, and derivatization of (N2)3- supported by lutetium complex. Initially, a (N2)3- radical, in [{(C5Me5){MeC(NiPr)2}Lu}2(μ2-η2:η2-N2)][K(crypt)] (crypt = 2,2,2-cryptand) complex, was generated through the reduction of neutral lutetium dinitrogen complex [{(C5Me5){MeC(NiPr)2}Lu}2(μ2-η2:η2-N2)] with potassium metal. Subsequently, the reaction of (N2)3- complex with methyl triflate (or triflic acid) led to the formation of an N-C (or N-H) bond, yielding the corresponding [{(C5Me5){MeC(NiPr)2}Lu}2(NN-R)(OTf)][K(crypt)] (R = Me, H, OTf = CF3SO3) as the product. Both electron paramagnetic resonance spectroscopy and density functional theory analyses support the radical character of the NN-Me unit. The Lu-N bonds in the (NN-Me)•2- radical complex are predominantly ionic, with 77% of the unpaired electron localized on the (NN-Me) fragment. Moreover, the geometry of the pure organic radical (NN-Me)•2-, optimized by double-hybrid density functional theory, closely matches that of the (NN-Me)•2- lutetium complex.

Dichloromethane as C1 Synthon for the Photoredox Catalytic Cyclopropanation of Aromatic Olefins.

Dichloromethane, as a readily available and inexpensive C1 synthon is proposed as a powerful building block for cyclopropanation of alkenes under mild conditions. Herein, we report a highly efficient and versatile dual photoredox system, involving a nickel aminopyridine coordination complex and a photocatalyst, for the cyclopropanation of aromatic olefins using dichloromethane, under visible-light irradiation. The cyclopropanation protocol has been successfully applied at gram scale. Mechanistic studies suggest a Ni(II) pyridyl radical complex as the key intermediate for the homolytic cleavage of the Csp3-Cl bond, generating a chloromethyl radical that is captured by the olefin coupling partner. Our findings also highlight the versatility of this methodology. By directing the radical/polar crossover process, we were able to selectively drive the reaction towards either the formation of cyclopropyl derivatives or the corresponding non-cyclic alkyl chloride products. The methodology also successfully apply to geminal dichloroalkanes, including the formation of spiro[2,2] compounds. Moreover, our methodology extends to the synthesis of deuterium-labelled cyclopropanes, demonstrating its utility in isotopic labelling and broadening its applicability in chemical synthesis and drug development.

Identifying Radical Pathways for Cu(I)/Cu(II) Relay Catalyzed Oxygenation via Online Coupled EPR/UV-Vis/Near-IR Monitoring.

Copper-catalyzed C─H oxygenation has drawn considerable attention in mechanistic studies. However, a comprehensive investigation combining radical pathways with a metal-catalytic cycle is challenged by the intricate organic radicals and metallic intermediates. Herein, an online coupled EPR/UV-vis/near-IR detecting method is developed to simultaneously monitor both reactive radical species and copper complex intermediates during the reaction. Focusing on copper-catalyzed phenol oxygenation with cumene hydroperoxide, the short-lived alkylperoxyl radical (EPR signal at g=2.0143) as well as the unexpected square planar Cu(II)-alkoxyl radical complex (near-IR signal at 833nm) are unveiled during the reaction, in addition to the observable phenoxyl radical in EPR, quinone product in UV-vis, and Cu(II) center in EPR. With a comprehensive picture of diverse intermediates evolving over the same timeline, a novel Cu(I)/Cu(II) proposed relay-catalyzed sequential radical pathway. In this sequence, Cu(II) activates hydroperoxide through Cu(II)-OOR into the alkylperoxide radical, while the reaction between Cu(I) and hydroperoxide leads to Cu(II)(•OR)OH with high H-atom abstracting activity. These results provide a thorough understanding of the Cu(I)/Cu(II) relay catalysis for phenol oxygenation, setting the stage for mechanistic investigations into intricate radical reactions promoted by metallic complexes.

Light Induced Cobalt(III) Carbene Radical Formation from Dimethyl Malonate As Carbene Precursor.

Radical-type carbene transfer catalysis is an efficient method for the direct functionalization of C-H and C=C bonds. However, carbene radical complexes are currently formed via high-energy carbene precursors, such as diazo compounds or iodonium ylides. Many of these carbene precursors require additional synthetic steps, have an explosive nature, or generate halogenated waste. Consequently, the utilization of carbene radical catalysis is limited by specific carbene precursors that access the carbene radical intermediate. In this study, we generate a cobalt(III) carbene radical complex from dimethyl malonate, which is commercially available and bench-stable. EPR and NMR spectroscopy were used to identify the intermediates and showed that the cobalt(III) carbene radical complex is formed upon light irradiation. In the presence of styrene, carbene transfer occurred, forming cyclopropane as the product. With this photochemical method, we demonstrate that dimethyl malonate can be used as an alternative carbene precursor in the formation of a cobalt(III) carbene radical complex.

N‒N hydrazonyl bond cleavage in benzothiazolyl-hydrazino-phenathrenequinone mediated by ruthenium(II) via an anion radical intermediate

The complexes [Ru(LBenz)H(CO)(PPh3)2] 2, [Ru(LBenz)Cl(CO)(PPh3)2] 3, (ligand behaving as bidentate monoanionic) and [Ru(LBenz)Cl(CO)(PPh3)] 4, (ligand is tridentate monoanionic) have been synthesized starting from benzothiazolyl-hydrazino-phenathrenequinone (HL) 1 and [RuH(CO)Cl(PPh3)3]. These are characterized by electrochemical and spectral methods as well as single crystal X-ray diffractometry (SCXRD). Upon treating with NaBH4, 3 accepts an electron within the coordinated ligand framework and the anionic hydrazonyl-N takes up a proton to be transformed to meta-stable hydrazinoquinone anion radical complex of ruthenium(II) [Ru(HLBenz•‒)Cl(CO)(PPh3)2] 5, possibly via concerted proton electron transfer process (CPET). Thus, the redox non-innocent character of the ligand upon complexation with ruthenium(II), has been disclosed and it is attributed to presence of low lying π* orbitals of almost entirely of phenanthraquinone and hydrazone character. In 5, the π‒acceptor ability of the ligand donor centres are reduced due to the existence of an odd electron in SOMO and hence the M-L distances around the coordination sphere are altered. The N‒N (hydrazonyl bond length increases from 1.296(6) Å in 3 to 1.429 Å in 5, leading to lesser thermodynamic stability of the latter and upon standing, the N‒N bond is cleaved to be transformed to 6+, possibly via the formation of iminoquinone anion radical complex, [6] (reported elsewhere). Also, it is via the dissociation of N‒N (hydrazonyl) bond, the biologically important molecule 2-aminobenzothiazole is formed along with 6+, so as to provide a novel route for its synthesis.

Three Novel Cyclic Zn(II)–Nitronyl Nitroxide Radical Complexes: Synthesis, Crystal Structures, and Properties

Three Novel Cyclic Zn(II)–Nitronyl Nitroxide Radical Complexes: Synthesis, Crystal Structures, and Properties