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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]

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]

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]

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]

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]

Osmium(II) PNP pincer complexes bearing a hemilabile pyridyl-pyrazolide (PyrPz) ligand have been synthesised, and their reactivity towards Lewis acidic bismuth compounds has been examined. Reactions with BiCl3 resulted in chlorine-atom-transfer to give an osmium(III) species. Reactions with cationic bismuth species led to adduct formation through N → Bi bond formation via the PyrPz ligand. Theoretical analyses revealed that steric interactions hamper Os → Bi bond formation and indicate that such interactions are possible upon reducing the steric profile around the osmium atom. Analytical techniques include NMR, IR, and EPR spectroscopy, cyclic voltammetry, elemental analysis and DFT calculations. [ABSTRACT FROM AUTHOR]

Reaction between 2-(2′-pyridyl)benzimidazole derivatives and [{IrCl(η5-C5Me5)}2(μ-Cl)2] afforded mono- and binuclear "piano-stool" Ir(III) compounds of type [IrnCln(η5-C5Me5)n(L)]Cln (n = 1, L = LET (1) and LSO3H (2); n = 2, L = LBN (3)), which were fully characterized, including the X-ray crystallographic analysis of 1. While the free ligands and compound 3 exhibited no toxicity to the tested microbes, compound 1 was highly potent against bacteria (MIC = 12.9–25.8 nM) and fungi (MIC < 0.40 nM). However, complex 1 induced damage to non-malignant cell lines (human embryonic kidney (HEK293), CC50 = 0.995 μg mL−1) and human RBCs (HC10 = 10.9 μg mL−1 and HC50 > 32 μg mL−1). Interestingly, complex 2, bearing the benzimidazole ligand with an alkylated sulfonate side chain (LSO3H), was selectively potent against C. neoformans with MIC value of 11.2 nM and was non-toxic to HEK293. According to DNA binding studies, compounds 1–3 could be considered as moderate metallo intercalators with a binding constant of 5.0 × 104–1.0 × 105 M−1. Alternatively, evidence was obtained, from ESI-MS measurements, for the non-covalent mode of binding of 2 to hen egg white lysozyme, while compounds 1 and 3 decomposed during the interaction with that protein. This may be attributed to the electrostatic and H-bonding interactions between the polar sulfonate group and charged protein side-chains. [ABSTRACT FROM AUTHOR]

Two surprising new outcomes of the reaction of Lewis bases with dihalodiboranes(4) are presented, including sp2–sp3 diboranes in which the Lewis base unit is bound to a highly sterically congested boron atom, and a rearranged double base adduct. The results provide a fuller understanding of the reactivity of diboranes, a poorly-understood class of molecule of critical importance to synthetic organic chemistry. [ABSTRACT FROM AUTHOR]

A heterocyclic manganese complex (4) derived from a carbonyl–borylene coupling reaction undergoes isomerisation, during which the former borylene moiety migrates to the cyclopentadienyl ligand and inserts into a C–H bond. This reaction and a computational study of its mechanism are discussed. [ABSTRACT FROM AUTHOR]

Reaction of different combinations of aryl(dihalo)boranes and trialkylsilyl iron metallates, a route previously used to prepare a terminal iron arylborylene complex, is found to lead to three distinct new reaction outcomes, including unselective decomposition, an inert iron(ii) (boryl)(silyl) complex, and a dinuclear bis(μ-silylene) complex. The latter result is to our knowledge the first example of a 1,2-alkylborane elimination, in contrast to the facile and ubiquitous 1,1-alkylborane elimination observed from (alkyl)(boryl) transition metal complexes, and is also a novel route to bridging silylene complexes. [ABSTRACT FROM AUTHOR]

Over the past decade, significant progress has been made in synthesizing atomically precise carbon nanostructures, particularly graphene nanoribbons (NRs), employing advanced synthetic methodologies. Despite these advancements, achieving control over the stereochemistry of twisted NRs has proven to be a formidable challenge. This manuscript presents a strategic approach to achieve absolute control over the single-handed helical conformation in a cove-edged NR. This strategy leverages enantiopure helicenes as a molecular wrench, intricately influencing the overall conformation of the NR. [7]helicenes stitched to the terminal K-regions of a conjugated pyrene NR through a stereospecific annulative π-extension reaction to produce a helically twisted NR with an end-to-end twist of 171°. Furthermore, a detailed investigation of the impact of twisting on the conformational population was studied by quantum chemical calculations., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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 B 2 Si 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.

A series of Pd(II) complexes of the general formula [PdX(NNS)] (X = Cl, Br, I, NCS and phenyl-tetrazole-thiolato; NNS = 2-quinolinecarboxyaldehyde- N 4 -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 IC 50 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.

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 (IC 50 = 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.

The cytotoxicity of two tricarbonyl Mn(I) complexes of the general formula fac -[MnBr(CO) 3 L] (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.

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.

Reaction between [RuCl 2 (CO) 2 ] n and 1 H -benzimidazol-2-ylmethyl-( N -phenyl)amine ligands (L R ) functionalized with various electron-donating and electron-withdrawing substituents on the phenyl ring (R = H, 4-CH 3 , 4-Cl, 4-COOCH 3 , and 3-COOCH 3 ) afforded the dark-stable photoactivatable carbon monoxide prodrugs of the general formula [RuCl 2 (CO) 2 L R ]. 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-COOCH 3 group (IC 50 = 45.08 ± 3.5 μM) are nontoxic under dark conditions. Upon illumination, all the compounds acquired cytotoxicity in the following order: H > 4-COOCH 3 > 4-CH 3 > 4-Cl > 3-COOCH 3 . 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.

The reactions of terminal acetylenes with doubly Lewis base-stabilised diborenes resulted in different outcomes depending on the nature of the ligands at boron and the conformation of the diborene (cyclic versus acyclic). N-heterocyclic carbene (NHC)-stabilised diborenes tended to undergo anti -selective hydroalkynylation at room temperature, whereas [2 + 2] cycloaddition was observed at higher temperatures, invariably followed by a C-N bond activation at one NHC ligand, leading to the ring-expansion of the initially formed BCBC ring and formation of novel boron-containing heterocycles. For phosphine-stabilised diborenes only [2 + 2] cycloaddition was observed, followed by a rearrangement of the resulting 1,2-dihydro-1,2-diborete to the corresponding 1,3-isomer, which amounts to complete scission of both the B[double bond, length as m-dash]B double and C[triple bond, length as m-dash]C triple bonds of the reactants. The elusive 1,2-isomer was finally trapped by using a cyclic phosphine-stabilised diborene, which prevented rearrangement to the 1,3-isomer. Extensive density functional theory (DFT) calculations provide a rationale for the selectivity observed., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

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.

Transition metal borylene complexes of the type [(OC)5M[double bond, length as m-dash]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).