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The photolytic or oxidative liberation of a cyclic (amino)(alkyl)carbene (CAAC)-stabilized arylborylene in the presence of organoazides yielded borylene-organoazide complexes (4a,b) has been achieved in a manner akin to the first step of the Staudinger reaction. Similarly, a CAAC-stabilized aminoborylene also afforded borylene-organoazide complexes (6a–c), which further undergo rearrangement to produce aminoborane triazene species (7a,b). [ABSTRACT FROM AUTHOR]

Borylation of a tungsten‐bound N2 ligand and halide abstraction provides access to a cationic complex with an unprecedented linear NNBR ligand. This complex undergoes [3+2] cycloaddition with azides, and an unexpected chain‐extension reaction with an iminoborane, leading to a complex with a five‐atom B/N chain. These two [NNBR]‐containing complexes, inorganic analogues of E. O. Fischer's alkynylcarbynes, are very rare examples of molecules containing all‐inorganic chains of sp‐hybridized atoms. [ABSTRACT FROM AUTHOR]

Borylierung eines wolframgebundenen N2‐Liganden und anschließende Halogenidabstraktion ermöglichen den Zugang zu einem kationischen Komplex mit einem bisher beispiellosen linearen NNBR‐Liganden. Dieser Komplex geht [3+2] Cycloadditionen mit Aziden ein und eine unerwartete Kettenverlängerungsreaktion mit einem Iminoboran, was zu einem Komplex mit einer fünfatomigen B/N‐Kette führt. Diese beiden [NNBR]‐haltigen Komplexe, anorganische Analoga von E. O. Fischers Alkinylcarbinen, sind sehr seltene Beispiele für Moleküle, die rein anorganische Ketten von sp‐hybridisierten Atomen enthalten. [ABSTRACT FROM AUTHOR]

Hydrosilanes undergo mild, uncatalyzed single and double 1,2-addition across the B–B triple bonds of diborynes, leading to an unsymmetrical silyldiborene and compounds with novel non-cluster three-membered B2Si rings. The reactions are a new addition to the very few catalyst- and alkali-metal-free methods available for the construction of B–Si bonds. [ABSTRACT FROM AUTHOR]

A series of Pd(II) complexes of the general formula [PdX(NNS)] (X = Cl, Br, I, NCS and phenyl-tetrazole-thiolato; NNS = 2-quinolinecarboxyaldehyde-N4-phenylthiosemicarbazone) was tested against four malignant cell lines for their antiproliferative properties and the outcomes were compared to those seen in normal mouse splenocytes. Various auxiliary ligands were substituted in order to investigate the impact of the character of the ligand on the cytotoxicity of this class of Pd(II) complexes. The iodo complex was the most cytotoxic compound towards the Caco-2 cell line in this study. The improved apoptosis and necrosis cell modes were in accordance with the fragmentation results of DNA, which revealed increased fragmentation terminals, especially in isothiocyanate and tetrazole-thiolato complexes. After 24 hours, at half the IC50 of each complex, the complex-treated cells exhibited considerable genotoxicity when compared to the corresponding non-treated control especially in the case of isothiocyanate and tetrazole-thiolato complexes. [ABSTRACT FROM AUTHOR]

The reaction of a pyridyl-substituted, doubly Lewis base-stabilised diborene with different amounts of copper(I) precursors led to the formation of the first chelating π-diborene complexes, the first π-diborene complexes in which metals are bound to both faces of the B＝B bond, and the first mixed-metal π-diborene species. [ABSTRACT FROM AUTHOR]

Human acute monocytic leukaemia cells were tested under both dark and light conditions for their susceptibility to Mn(I) and Ru(II) carbonyl complexes with a diphenyl pyridyl phosphine coligand. The Ru(II) complex (IC50 = 7.13 ± 0.8 μM) displayed higher outstanding potency against leukaemia than the Mn(I) analogue (54.58 ± 4.1 μM) in the dark and both complexes were completely harmless to healthy mouse bone marrow cells. [ABSTRACT FROM AUTHOR]

In this contribution, we reported the three‐dimensional (3D) analogues of N‐heterocyclic carbene (NHC)‐stabilized 9‐borafluorenium and 9‐borafluorene radical. The radical was fully characterized by cyclic voltammetry (CV), UV‐Vis absorption spectroscopy, electron paramagnetic resonance (EPR) and single‐crystal X‐ray diffraction analyses. The distinct boron‐centered radical character of 9‐borafluorene radical was corroborated by DFT calculations and EPR analysis. [ABSTRACT FROM AUTHOR]

Author(s): Holger Braunschweig (corresponding author) [1]; Rian D. Dewhurst [1]; Florian Hupp [1]; Marco Nutz [1]; Krzysztof Radacki [1]; Christopher W. Tate [1]; Alfredo Vargas [2]; Qing Ye [1] The [...]

The synthesis and characterization of laterally extended azabora[5]‐, ‐[6]‐ and ‐[7]helicenes, assembled from N‐heteroaromatic and dibenzo[g,p]chrysene building blocks is described. Formally, the π‐conjugated systems of the pristine azaborole helicenes were enlarged with a phenanthrene unit leading to compounds with large Stokes shifts, significantly enhanced luminescence quantum yields (Φ) and dissymmetry factors (glum). The beneficial effect on optical properties was also observed for helical elongation. The combined contributions of lateral and helical extensions resulted in a compound showing green emission with Φ of 0.31 and |glum| of 2.2×10−3, highest within the series of π‐extended azaborahelicenes and superior to emission intensity and chiroptical response of its non‐extended congener. This study shows that helical and lateral extensions of π‐conjugated systems are viable strategies to improve features of azaborole helicenes. In addition, single crystal X‐ray analysis of configurationally stable [6]‐ and ‐[7]helicenes was used to provide insight into their packing arrangements. [ABSTRACT FROM AUTHOR]

The cytotoxicity of two tricarbonyl Mn(I) complexes of the general formula fac-[MnBr(CO)3L] (L = quinoline-2-carboxaldehyde (A) and 8-amino quinoline (B)) towards triple negative breast cancer (MDA-MB-231) was reported. Complexes A and B released CO when exposed to 468 nm light. Compound B has a dose-dependent cytotoxicity, with half maximal inhibitory concentration values of 19.62 μM and 11.43 μM before and after illumination, respectively. Co-treatment of MDA-MB-231 with paclitaxel (30 nM) and complex B (10 μM) resulted in a 50% reduction in cell viability. [ABSTRACT FROM AUTHOR]

The installation of electron-withdrawing functional groups at the carbocyclic backbone of aminotroponiminate (ATI) ligands is a versatile method for influencing the electronic properties of the resulting ATI complexes. We report here Li, Na, and K salts of an ATI ligand with a phenylsulfinyl substituent in the backbone. It is demonstrated that the sulfinyl group actively contributes to the coordination chemistry of these complexes, effectively competing with neutral donor ligands such as thf or pyridine in the solid state (XRD), in solution (DOSY NMR spectroscopy), and in the gas phase (DFT). The impact of the phenylsulfinyl group on the redox properties of the complexes have been investigated and access to sodium sodiate species through ligand-induced disproportionation has been studied. Transfer of the ATI ligand to the heavy p-block element bismuth has been demonstrated. Analytical techniques applied in this work include multinuclear and DOSY NMR spectroscopy, cyclic voltammetry, DFT calculations, and single-crystal X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]

The oxidation of doubly cyclic alkyl(amino)carbene-stabilised closed-shell 1,4-diborabenzene with sulfur or selenium yields S4/S5- or Se4-bridged hexa-1,4-dienes, respectively, whereas that of the related open-shell singlet biradical 9,10-diboraanthracene with O2, sulfur or selenium yields the endoperoxo- or S/Se-bridged bicyclic species, respectively. [ABSTRACT FROM AUTHOR]

Reaction between [RuCl2(CO)2]n and 1H-benzimidazol-2-ylmethyl-(N-phenyl)amine ligands (LR) functionalized with various electron-donating and electron-withdrawing substituents on the phenyl ring (R = H, 4-CH3, 4-Cl, 4-COOCH3, and 3-COOCH3) afforded the dark-stable photoactivatable carbon monoxide prodrugs of the general formula [RuCl2(CO)2LR]. Release of the CO molecules from the Ru(II) compounds was examined by monitoring the electronic and IR spectra upon illumination at 365 nm. A noticeable decrease in the intensities of the two characteristic ν(C≡O) modes for Ru(CO) II2 species, and the growth of two new bands for the mono-carbonyl species and free CO, were the main features of the photolysis profiles. The cytotoxicity of the complexes towards breast cancer (MCF-7) cells was assessed with and without illumination at 365 nm. All the complexes except that with a 4-COOCH3 group (IC50 = 45.08 ± 3.5 μM) are nontoxic under dark conditions. Upon illumination, all the compounds acquired cytotoxicity in the following order: H > 4-COOCH3 > 4-CH3 > 4-Cl > 3-COOCH3. Investigation of the cytotoxicity of the CO-depleted fragments showed that the light-induced cytotoxicity can be attributed to the liberated CO and CO-depleted metal fragments, including the liberated benzimidazole ligands. [ABSTRACT FROM AUTHOR]

In this communication, we demonstrate a novel approach to prepare a discrete dimer of chiral phthalocyanine (Pc) by exploiting the flexible molecular geometry of helicenes, which enables structural interlocking and strong aggregation tendency of Pcs. Synthesized [7]helicene‐Pc hybrid molecular structure, zinc‐[7]helicenocyanine (Zn‐7HPc), exclusively forms a stable dimeric pair consisting of two homochiral molecules. The dimerization constants were estimated to be as high as 8.96×106 M−1 and 3.42×107 M−1 in THF and DMSO, respectively, indicating remarkable stability of dimer. In addition, Zn‐7HPc exhibited chiral self‐sorting behavior, which resulted in preferential formation of a homochiral dimer also in the racemic sample. Two phthalocyanine subunits in the dimeric form strongly communicate with each other as revealed by a large comproportionation constant and observation of an IV‐CT band for the thermodynamically stable mixed‐valence state. [ABSTRACT FROM AUTHOR]

In dieser Publikation stellen wir einen neuartigen Ansatz zur Herstellung eines diskreten Dimers aus chiralem Phthalocyanin (Pc) vor, wobei wir die flexible Molekülgeometrie von Helicenen nutzen, die eine strukturelle Vernetzung und eine starke Aggregationstendenz von Pcs ermöglicht. Die synthetisierte [7]Helicen‐Pc‐Hybrid‐Molekularstruktur, Zink‐[7]Helicenocyanin (Zn‐7HPc), bildet ausschließlich ein stabiles Dimer aus zwei homochiralen Molekülen. Die Dimerisierungskonstanten wurden auf 8.96×106 M−1 bzw. 3.42×107 M−1 in THF bzw. DMSO geschätzt, was auf eine bemerkenswerte Stabilität des Dimers hindeutet. Darüber hinaus zeigt Zn‐7HPc ein chirales Selbstorganisationsverhalten, so dass sich auch in der racemischen Probe bevorzugt ein homochirales Dimer bildet. Die zwei Phthalocyanin‐Untereinheiten in der dimeren Form interagieren stark miteinander, was sich in einer großen Komproportionierungskonstante und der Beobachtung einer IV‐CT‐Bande für den thermodynamisch stabilen gemischt‐valenten Zustand zeigt. [ABSTRACT FROM AUTHOR]

A systematic study on Lewis‐acid/base adducts of N‐heterocyclic carbenes (NHCs) and the cyclic (alkyl)(amino)carbene cAACMe (1‐(2,6‐di‐iso‐propylphenyl)‐3,3,5,5‐tetramethyl‐pyrrolidin‐2‐ylidene) with antimony(III) chlorides of the general formula SbCl2R (R=Cl, Ph, Mes) is presented. The reaction of the NHCs Me2ImMe (1,3,4,5‐tetra‐methyl‐imidazolin‐2‐ylidene), iPr2ImMe (1,3‐di‐isopropyl‐4,5‐dimethyl‐imidazolin‐2‐ylidene), Mes2Im, Dipp2Im (R2Im=1,3‐di‐organyl‐imidazolin‐2‐ylidene; Mes=2,4,6‐trimethylphenyl, Dipp=2,6‐di‐isopropylphenyl) and cAACMe with antimony(III) compounds SbCl2R (R=Cl (1), Ph (2) and Mes (3)) yields the adducts NHC ⋅ SbCl2R (R=Cl (4), Ph (5) and Mes (6); NHC=Me2ImMe (a), iPr2ImMe (b), Dipp2Im (c) and Mes2Im (d)) and cAACMe ⋅ SbCl2R (R=Cl (4 e) and Ph (5 e)). Thermal treatment of (Dipp2Im) ⋅ SbCl2Ar (Ar=Ph (5 c) and Mes (6 c)) in benzene leads to isomerization to the backbone coordinated aNHC‐adduct aDipp2Im ⋅ SbCl2Ar (Ar=Mes (7) and Ph (8)) ("a" denotes "abnormal" coordination mode of the NHC) in high yields. One of the chloride substituents at antimony of 7 can be abstracted by GaCl3 or Ag[BF4] to obtain the imidazolium salts [aDipp2Im ⋅ SbClMes][BF4] (9) and [aDipp2Im ⋅ SbClMes][GaCl4] (10). [ABSTRACT FROM AUTHOR]

Aminotroponiminate (ATI) ligands are a versatile class of redox‐active and potentially cooperative ligands with a rich coordination chemistry that have consequently found a wide range of applications in synthesis and catalysis. While backbone substitution of these ligands has been investigated in some detail, the impact of electron‐withdrawing groups on the coordination chemistry and reactivity of ATIs has been little investigated. We report here Li, Na, and K salts of an ATI ligand with a nitro‐substituent in the backbone. It is demonstrated that the NO2 group actively contributes to the coordination chemistry of these complexes, effectively competing with the N,N‐binding pocket as a coordination site. This results in an unprecedented E/Z isomerisation of an ATI imino group and culminates in the isolation of the first "naked" (i. e. without directional bonding to a metal atom) ATI anion. Reactions of sodium ATIs with silver(I) and tritylium salts gave the first N,N‐coordinated silver ATI complexes and unprecedented backbone substitution reactions. Analytical techniques applied in this work include multinuclear (VT‐)NMR spectroscopy, single‐crystal X‐ray diffraction analysis, and DFT calculations. [ABSTRACT FROM AUTHOR]

Introduction of the propyl-sulfonic acid group at N1 of the coordinated 2-(2-pyridyl)benzimidazole ligand (L) in [RhCl(η5-C5Me5)L](CF3SO3) gives rise to a water-soluble complex, which can bind to the model protein lysozyme via non-covalent interactions. The complex shows selective moderate toxicity against Cryptococcus neoformans (MIC = 21.6–43.3 μM) and exhibits no cytotoxicity to healthy HEK293 cells. [ABSTRACT FROM AUTHOR]

Boroles are attracting broad interest for their myriad and diverse applications, including in synthesis, small molecule activation and functional materials. Their properties and reactivity are closely linked to the cyclic conjugated diene system, which has been shown to participate in cycloaddition reactions, such as the Diels‐Alder reaction with alkynes. The reaction steps leading to boranorbornadienes, borepins and tricyclic boracyclohexenes from the thermal reaction of boroles with alkynes are seemingly well understood as judged from the literature. Herein, we question the long‐established mechanistic picture of pericyclic rearrangements by demonstrating that seven‐membered borepins (i. e. heptaphenylborepin and two derivatives substituted with a thienyl and chloride substituent on boron) exist in a dynamic equilibrium with the corresponding bicyclic boranorbornadienes, the direct Diels‐Alder products, but are not isolable products from the reactions. Heating gradually converts the isomeric mixtures into fluorescent tricyclic boracyclohexenes, the most stable isomers in the series. Results from mechanistic DFT calculations reveal that the tricyclic compounds derive from the boranorbornadienes and not the borepins, which were previously believed to be intermediates in purely pericyclic processes. [ABSTRACT FROM AUTHOR]

Cyclic alkyl(amino)carbene‐stabilized (cyano)hydroboryl anions were synthesized by deprotonation of (cyano)dihydroborane precursors. While they display boron‐centered nucleophilic reactivity towards organohalides, generating fully unsymmetrically substituted cyano(hydro)organoboranes, they show cyano‐nitrogen‐centered nucleophilic reactivity towards haloboranes, resulting in the formation of hitherto unknown linear 2‐aza‐1,4‐diborabutatrienes. [ABSTRACT FROM AUTHOR]

The behavior of the redox‐active aminotroponiminate (ATI) ligand in the coordination sphere of bismuth has been investigated in neutral and cationic compounds, [Bi(ATI)3] and [Bi(ATI)2Ln][A] (L=neutral ligand; n=0, 1; A=counteranion). Their coordination chemistry in solution and in the solid state has been analyzed through (variable‐temperature) NMR spectroscopy, line‐shape analysis, and single‐crystal X‐ray diffraction analyses, and their Lewis acidity has been evaluated by using the Gutmann–Beckett method (and modifications thereof). Cyclic voltammetry, in combination with DFT calculations, indicates that switching between ligand‐ and metal‐centered redox events is possible by altering the charge of the compounds from 0 in neutral species to +1 in cationic compounds. This adds important facets to the rich redox chemistry of ATIs and to the redox chemistry of bismuth compounds, which is, so far, largely unexplored. [ABSTRACT FROM AUTHOR]

The concepts of aromaticity and antiaromaticity have a long history, and countless demonstrations of these phenomena have been made with molecules based on elements from the p, d, and f blocks of the periodic table. In contrast, the limited oxidation‐state flexibility of the s‐block metals has long stood in the way of their participation in sophisticated π‐bonding arrangements, and truly antiaromatic systems containing s‐block metals are altogether absent or remain poorly defined. Using spectroscopic, structural, and computational techniques, we present herein the synthesis and authentication of a heterocyclic compound containing the alkaline earth metal beryllium that exhibits significant antiaromaticity, and detail its chemical reduction and Lewis‐base‐coordination chemistry. [ABSTRACT FROM AUTHOR]

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The one‐electron reduction of a cyclic (alkyl)(amino)carbene (CAAC)‐stabilized arylborylene carbonyl complex yields a dimeric borylketyl radical anion, resulting from an intramolecular aryl migration to the CO carbon atom. Computational analyses support the existence of a [(CAAC)B(CO)Ar].− radical anion intermediate. Further reduction leads to a highly nucleophilic dianionic (boraneylidene)methanolate. [ABSTRACT FROM AUTHOR]

Copyright of Angewandte Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The lysozyme binding affinity and the electronic properties of [ReX(CO)3(terpy-κ2N1,N2)] (X = Br− and triazolateCOOCH2CH3,CF3) were reported. The triazolate complex was prepared in a [3 + 2] cycloaddition click reaction. The bromo compound reacted with lysozyme affording adducts with Re(CO)3+ fragments, while the triazolate compound persisted. A red shift of the MLCT band of the triazolate compound in progressively less polar solvents may be due to the negative solvatochromism. [ABSTRACT FROM AUTHOR]

Transition metal borylene complexes of the type [(OC)5M＝BN(SiMe3)(tBu)] (M = Cr, Mo, W) have been synthesised by salt elimination of the corresponding dibromoborane and the dianionic metallates Na2[M(CO)5]. The borylene complexes have been characterised by multinuclear solution-state NMR spectroscopy and solid-state molecular structure determination. The group 6 borylene complexes can be used to effectively transfer the borylene ligand to other transition metal complexes by replacing one or two carbonyl ligands upon irradiation of the reaction mixture with UV light. This borylene transfer reaction led to the formation of new terminal and bridging borylene complexes which cannot be formed by the corresponding salt elimination reactions, including a rare example of a bis(terminal borylene) complex and only the second reported terminal borylene complex of an early transition metal (vanadium). [ABSTRACT FROM AUTHOR]

The reductive coupling of an N‐heterocyclic carbene (NHC) stabilized (dibromo)vinylborane yields a 1,2‐divinyldiborene, which, although isoelectronic to a 1,3,5‐triene, displays no extended π conjugation because of twisting of the C2B2C2 chain. While this divinyldiborene coordinates to copper(I) and platinum(0) in an η2‐B2 and η4‐C2B2 fashion, respectively, it undergoes a complex rearrangement to an η4‐1,3‐diborete upon complexation with nickel(0). [ABSTRACT FROM AUTHOR]