Adduct formation of [(η7-C7H7)Hf(η5-C5H5)] with isocyanides,phosphines and N-heterocyclic carbenes: An experimental and theoretical study

The reactions of [(η⁷-C₇H₇)Hf(η⁵-C₅H₅)] (1b) with the two-electron donor ligands tert-butyl isocyanide (tBuNC), 2,6-dimethylphenyl isocyanide (XyNC), 1,3,4,5-tetramethylimidazolin-2-ylidene (IMe) and trimethylphosphine (PMe₃) are reported. The 1:1 complexes [(η⁷-C₇H₇)Hf(η⁵-C₅H₅)L] (2b, L = tBuNC; 3b, L = XyNC; 4b, L = IMe, 5b, L = PMe₃) have been isolated in crystalline form, and their molecular structures have been determined by X-ray diffraction analyses. The stabilities of these hafnium complexes were probed via spectroscopic and theoretical methods, and the results were compared to those previously reported for the corresponding zirconium complexes derived from [(η⁷-C₇H₇)Zr(η⁵-C₅H₅)] (1a). The X-ray crystal structure of the PMe₃ adduct [(η⁷-C₇H₇)Zr(η⁵-C₅H₅)(PMe₃)] (5a) was also established.     

Heteroleptic half-sandwich Ru(II), Rh(III) and Ir(III) complexes based on 5-ferrocenyldipyrromethene

The synthesis and characterization of heteroleptic complexes with the formulations [(η⁶-arene)RuCl(fcdpm)] (η⁶-arene = C₆H₆, C₁₀H₁₄) and [(η⁵-C₅Me₅)MCl(fcdpm)] (M = Rh, Ir; fcdpm = 5-ferrocenyldipyrromethene) have been reported. All the complexes have been characterized by elemental analyses, IR, ¹H NMR and electronic spectral studies. Structures of [(η⁶-C₆H₆)RuCl(fcdpm)] and [(η⁶-C₁₀H₁₄)RuCl(fcdpm)] have been determined crystallographically. Chelating monoanionic linkage of fcdpm to the respective metal centres has been supported by spectral and structural studies. Further, reactivity of the representative complex [(η⁶-C₁₀H₁₄)RuCl(fcdpm)] with ammonium thiocyanate (NH₄SCN) and triphenylphosphine (PPh₃) have been examined.     

Ruthenium tetrazene complexes bearing glucose moieties on their periphery: Synthesis,characterization, and in vitro cytotoxicity

Ruthenium tetrazene complexes with general formula [Cp*RuCl(1,4-R₂N₄)] (Cp* = η⁵-C₅Me₅), where R = benzyl ( 1 ), 2-fluorobenzyl ( 2 ), β-d -glucopyranosyl-unprotected ( 3a ) and acyl-protected ( 3b – d ), 2-acetamido-β-d -glucopyranosyl-unprotected ( 4a ) and acyl-protected ( 4b – d ), propyl-β-d -glucopyranoside-unprotected ( 5a ), and O-acetylated ( 5b ), were synthesized and characterized using nuclear magnetic resonance and electrospray ionization–mass spectrometry. In addition, the molecular structure of 3b was determined using X-ray crystallography. The cytotoxicity of complexes against ovarian (A2780, SK-OV-3) and breast (MDA-MB-231) cancer cell lines and noncancerous cell line HEK-293 was evaluated and compared to cisplatin activity. The carbohydrate-modified complexes bearing acyl-protecting groups exhibited higher efficacy (in low micromolar range) than unprotected ones, where the most active 4d was superior to cisplatin up to five times against all investigated cancer cell lines; however, no significant selectivity was achieved. The complex induced apoptotic cell death at low micromolar concentrations (0.5 μM for A2780 and HEK293; 2 μM for SK-OV-3 and MDA-MB-231).     

Lysosome‐targeted potent half‐sandwich iridium(III) α‐diimine antitumor complexes

Fifteen organometallic Ir(III) half‐sandwich complexes ( 1A – 5C ) having the general formula [(η⁵‐Cp^x)Ir(N^N)Cl]PF₆ (Cp^x = Cp*, tetramethyl(phenyl)cyclopentadienyl (Cp^xph) or tetramethyl(biphenyl)cyclopentadienyl (Cp^xbiph); N^N = diamine) have been synthesized and characterized. The molecular structure of 1A was determined using single‐crystal X‐ray diffraction analysis. The hydrolysis of 1A – 5C was monitored using UV–visible spectra. Complexes 3A – 3C showed catalytic activity for the oxidation of NADH to NAD⁺, where 3C showed the highest turnover number of 29.9 within 450 min. Cytotoxicity examination by MTT assay was carried out against two human cancer cell lines (HeLa and A549) after 24 or 48 h drug treatment. The complexes showed high potency, where the most potent complex ( 3C ; IC₅₀ = 3.4 μM) was six times more active than cisplatin against A549 cells after 24 h drug exposure. Cytotoxic potency towards A549 cells increased with phenyl substitution on Cp ring: Cp^xbiph > Cp^xph > Cp*. In addition, the biological studies showed that 3C caused cell apoptosis and cell cycle arrest at G₁ phase in A549 cancer cells. Moreover, 3C increased the level of reactive oxygen species markedly after 24 h, which may provide an important basis for killing cancer cells. Confocal laser scanning microscopy was used to track 3C in A549 cells. The cellular localization experiment showed that 3C targeted lysosomes and caused lysosomal damage.     

Neutral and cationic half‐sandwich arene d6 metal complexes containing pyridyl and pyrimidyl thiourea ligands with interesting bonding modes: Synthesis,structural and anti‐cancer studies

The reaction of [(p‐cymene)RuCl₂]₂ and [Cp*MCl₂]₂ (M = Rh/Ir) with benzoyl (2‐pyrimidyl) thiourea (L1) and benzoyl (4‐picolyl) thiourea (L2) led to the formation of cationic complexes bearing formula [(arene) M (L1)к² _(N,S) Cl]⁺ and [(arene) M (L2)к²_(N,S)Cl]⁺ [(arene) = p‐cymene, M = Ru, ( 1 , 4 ); Cp*, M = Rh ( 2 , 5 ) and Ir ( 3 , 6 )]. Precursor compounds reacted with benzoyl (6‐picolyl) thiourea (L3) affording neutral complexes having formula [(arene) M (L3)к¹_(S)Cl₂] [arene = p‐cymene, M = Ru, ( 7 ); Cp*, M = Rh ( 8 ), Ir ( 9 )]. X‐ray studies revealed that the methyl substituent attached to the pyridine ring in ligands L2 and L3 affects its coordination mode. When methyl group is at the para position of the pyridine ring (L2), the ligand coordinated metal in a bidentate chelating N, S‐ mode whereas methyl group at ortho position (L3), it coordinated in a monodentate mode. Further the anti‐cancer studies of the thiourea derivatives and its complexes carried out against HCT‐116, HT‐29 (human colorectal cancer), Mia‐PaCa‐2 (human pancreatic cancer) and ARPE‐19 (non‐cancer retinal epithelium) cell lines showed that the thiourea ligands are inactive but upon complexation, the metal compounds displayed potent and selective activity against cancer cells in vitro. Iridium complexes were found to be more potent as compared to ruthenium and rhodium complexes.     

Half‐sandwich ruthenium,rhodium and iridium complexes featuring oxime ligands: Structural studies and preliminary investigation of in vitro and in vivo anti‐tumour activities

Half‐sandwich ruthenium, rhodium and iridium complexes ( 1 – 12 ) were synthesized with aldoxime ( L1 ), ketoxime ( L2 ) and amidoxime ( L3 ) ligands. Ligands have the general formula [PyC(R)NOH], where R = H ( L1 ), R = CH₃ ( L2 ) and R = NH₂ ( L3 ). Reaction of [{(arene)MCl₂}₂] (arene = p ‐cymene, benzene, Cp*; M = Ru, Rh, Ir) with ligands L1 – L3 in 1:2 metal precursor‐to‐ligand ratio yielded complexes such as [{(arene)MLκ²_(N∩N)Cl}]PF₆. All the ligands act as bidentate chelating nitrogen donors in κ²_(N∩N) fashion while forming complexes. In vitro anti‐tumour activity of complexes 2 and 10 against HT‐29 (human colorectal cancer), BE (human colorectal cancer) and MIA PaCa‐2 (human pancreatic cancer) cell lines and non‐cancer cell line ARPE‐19 (human retinal epithelial cells) revealed a comparable activity although complex 2 demonstrated greater selectivity for MIA PaCa‐2 cells than cisplatin. Further studies demonstrated that complexes 3 , 6 , 9 and 12 induced significant apoptosis in Dalton's ascites lymphoma (DL) cells. In vivo anti‐tumour activity of complex 2 on DL‐bearing mice revealed a statistically significant anti‐tumour activity (P  = 0.0052). Complexes 1 – 12 exhibit HOMO–LUMO energy gaps from 3.31 to 3.68 eV. Time‐dependent density functional theory calculations explain the nature of electronic transitions and were in good agreement with experiments.     

Bonding situation and stability of η1- and η6-bonded heteroarene complexes M(η1-EC5H5)6 and M(η6-EC5H5)2 (M = Cr,Mo, W; E = N,P, As,Sb, Bi)

Density functional calculations at the BP86/TZ2P level are reported for the pseudo-octahedral heteroarene complexes M(η¹-EC₅H₅)₆ and for the sandwich complexes M(η⁶-EC₅H₅)₂ (M = Cr, Mo, W; E = N, P, As, Sb, Bi). The complexes M(CO)₆ and M(η⁶-C₆H₆)₂ have been calculated for comparison. The nature of the metal–ligand interactions was analyzed with the EDA (energy decomposition analysis) method. The calculated bond dissociation energies (BDE) of M(η¹-EC₅H₅)₆ have the order for E = P > As > N > Sb ? Bi and for M = Cr < Mo < W. All hexaheteroarenes bind more weakly than CO in M(CO)₆. Except for pyridine, which is the weakest η⁶-bonded ligand, the trend in the BDE of the M(η⁶-EC₅H₅)₂ complexes is opposite to the trend of the M(η¹-EC₅H₅)₆ complexes NC₅H₅ < PC₅H₅ < AsC₅H₅ < SbC₅H₅ < BiC₅H₅. The opposite trend is explained with the different binding modes in M(η⁶-EC₅H₅)₂ and M(η¹-EC₅H₅)₆. The bonding in the former complexes mainly takes place through the π electrons of the ligand which are delocalized over the ring atoms while the bonding in the latter takes place through the lone-pair electrons of the heteroatoms E. The Lewis basicity of the group-15 heterobenzenes EC₅H₅ becomes weaker for the heavier elements E. The occupied π orbitals of the heterobenzene ring become gradually more polarized toward the five carbon atoms in the heavier arenes EC₅H₅ which induces stronger metal-carbon bonds in M(η⁶-EC₅H₅)₂ and weaker metal-E bonds. The EDA calculations show that the nature of the M-EC₅H₅ bonding in M(η¹-EC₅H₅)₆ is similar to the M–CO bonding in M(CO)₆. Both types of bonds have a slightly more covalent than electrostatic character. The π orbital interactions in the chromium and molybdenum complexes of CO and heterobenzene are more important than the σ interactions. This holds true also for the tungsten complexes of CO and the lighter heteroarenes while the σ- and π-bonding in the heavier W(η¹-EC₅H₅)₆ species have similar strength. The EDA results also show that the nature of the bonding in the sandwich complexes M(η⁶-EC₅H₅)₂ is very similar to the bonding in the bisbenzene complexes M(η⁶-C₆H₆)₂. The orbital interactions contribute for all metals and all arene ligands about 60% of the attractive interactions while the electrostatic attraction contributes about 40%. The largest contribution to the orbital term comes always from the δ orbitals. The calculations predict that the relative stability of the sandwich complexes M(η⁶-EC₅H₅)₂ over the octahedral species M(η¹-EC₅H₅)₆ increases when E becomes heavier and it increases from W to Mo to Cr when E = N, P, As.     

Cationic organoiron mixed-sandwich hydrazine complexes: Reactivity toward aldehydes,ketones, β-diketones and dioxomolybdenum complexes

This review covers comprehensively the authors work during the present decade based on the chemistry of ionic organometallic hydrazines formulated as [(η⁵-Cp′)Fe(η⁶-Ar-NHNH₂)]⁺PF₆^? (Cp′ = C₅H₅, C₅Me₅; Ar = aryl), that could be considered as a new generation of hydrazines owing to the changes provoked by the coordination of the 12-electron Cp′Fe⁺ fragment both in the electronic properties of the aromatic ring and in the hydrazine group. The reactivity of this new class of hydrazine is obviously centered, as in the classic Fischer's organohydrazines, Ar-NHNH₂, on the –NHNH₂ functional unit which is able to react with aldehydes, RCH(O) (R = alkyl, aryl, ferrocenyl (Fc)) and ketones, RR′CO (R = alkyl, aryl; R′ = alkyl, aryl, Fc), to afford ionic organometallic hydrazones. Likewise, the mixed-sandwich hydrazine precursors react with β-diketones Me–C(O)–CH₂–C(O)–Me to afford ionic organometallic pyrazoles, and with cis-dioxo-molybdenum complexes, e.g. [MoO₂(S₂CNEt₂)₂], to afford ionic organometallic mono-organodiazenido complexes in which the two metal centers are connected by a μ,η⁶:η¹-aryldiazenido bridge. While some ionic hydrazones exhibit NLO properties, the ionic organodiazenido hybrid complexes exhibit charge-transfer features.     

Spectroscopic and electrochemical study for evaluating DNA interaction activity of 4‐(3‐halophenyl)‐6‐(pyridin‐2‐yl)pyrimidin‐2‐amine based piano stool Cp* Rh (III) and Ir (III) complexes

Six novel organometallic half sandwich complexes [(η5‐C₅Me₅)M(L^1–3)Cl]Cl.2H₂O were synthesized using [{(η⁵‐C₅Me₅)M(μ‐Cl)Cl₂], where M = Ir (III)/Rh (III) and L^1–3 = three pyridyl pyrimidine based ligands; and characterized by NMR, Infra‐red spectroscopy, conductance, elemental and thermal analysis. The complex‐DNA binding mode and/or strength evaluated using absorption titration, electrochemical studies and hydrodynamic measurement proposed intercalative binding mode, which was also confirmed by molecular docking study. Differential pulse voltammetry and cyclic voltammetry studies indicated an alteration in oxidation and reduction potentials of complexes (M⁺⁴/M⁺³) in presence of CT‐DNA. The metal complexes can cleave plasmid DNA as proposed in gel electrophoretic analysis. The LC₅₀ values of complexes evaluated on brine shrimp suggested their potent cytotoxic nature.     

Preparation and characterization of Cp-functionalized cycloheptatrienyl–cyclopentadienyl titanium sandwich complexes (troticenes)

Cp-functionalized monotroticenes [(η⁷-C₇H₇)Ti(η⁵-C₅H₄E)] (2, E = Ph₂SiCl; 3, E = tBu₂SnCl; 12, E = I) and bitroticenes [(η⁷-C₇H₇)Ti(η⁵-C₅H₄)]₂E′ (5, E′ = PPh; 6, E′ = BN(SiMe₃)₂; 7, E′ = Cp₂Ti) were prepared by salt elimination metathesis between the monolithiated troticene [(η⁷-C₇H₇)Ti(η⁵-C₅H₄Li)]·pmdta (1b) (pmdta = N,N′,N′,N″,N″-pentamethyldiethylene-triamine) and the appropriate electrophile. The troticenyl-substituted zirconocene monochloride [(η⁷-C₇H₇)Ti(η⁵-C₅H₄ZrClCp*₂)] (Cp* = η⁵-C₅Me₅) (8) and hafnocene ethoxide [(η⁷-C₇H₇)Ti{η⁵-C₅H₄Hf(OEt)Cp₂}] (Cp = η⁵-C₅H₅) (11), and the heterobimetallic μ-oxo complexes [(η⁷-C₇H₇)Ti(η⁵-C₅H₄MCp₂)]₂O (9, M = Zr; 10, M = Hf) were obtained instead of the expected zircona- and hafna[1]troticenophanes by reaction of the dilithiated troticene [(η⁷-C₇H₆Li)Ti(η⁵-C₅H₄Li)]·pmdta (1a) with [Cp₂MCl₂] (M = Zr, Hf) or [Cp*₂ZrCl₂] in stoichiometric amounts. These compounds were characterized by single crystal X-ray diffraction analyses and, in the case of 2, 3, 5–7, 9, 10 and 12, also by elemental analyses and ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. Exposure of the troticenyl organotin chloride 3 to moisture resulted in its partial hydrolysis and formation of the organostannoxane-bridged bitroticene 4, while palladium-catalyzed Negishi C–C cross-coupling reaction between the troticenylzinc chloride [(η⁷-C₇H₇)Ti(η⁵-C₅H₄ZnCl)] (13) and the iodotroticene 12 or iodobenzene (PhI) led to the fulvalene complexes [(η⁷-C₇H₇)Ti(η⁵-C₅H₄)]₂ (14) and [(η⁷-C₇H₇)Ti(η⁵-C₅H₄Ph)] (15). Compound 4 displays an unsymmetrical structure with the troticenyl fragments cis with respect to the Sn–O–Sn core, whereas compound 14 is centrosymmetrically trans oriented.     

Preparation and characterization of Cp-functionalized cycloheptatrienyl–cyclopentadienyl titanium sandwich complexes (troticenes)

Cp-functionalized monotroticenes [(η⁷-C₇H₇)Ti(η⁵-C₅H₄E)] (2, E = Ph₂SiCl; 3, E = tBu₂SnCl; 12, E = I) and bitroticenes [(η⁷-C₇H₇)Ti(η⁵-C₅H₄)]₂E′ (5, E′ = PPh; 6, E′ = BN(SiMe₃)₂; 7, E′ = Cp₂Ti) were prepared by salt elimination metathesis between the monolithiated troticene [(η⁷-C₇H₇)Ti(η⁵-C₅H₄Li)]·pmdta (1b) (pmdta = N,N′,N′,N″,N″-pentamethyldiethylene-triamine) and the appropriate electrophile. The troticenyl-substituted zirconocene monochloride [(η⁷-C₇H₇)Ti(η⁵-C₅H₄ZrClCp*₂)] (Cp* = η⁵-C₅Me₅) (8) and hafnocene ethoxide [(η⁷-C₇H₇)Ti{η⁵-C₅H₄Hf(OEt)Cp₂}] (Cp = η⁵-C₅H₅) (11), and the heterobimetallic μ-oxo complexes [(η⁷-C₇H₇)Ti(η⁵-C₅H₄MCp₂)]₂O (9, M = Zr; 10, M = Hf) were obtained instead of the expected zircona- and hafna[1]troticenophanes by reaction of the dilithiated troticene [(η⁷-C₇H₆Li)Ti(η⁵-C₅H₄Li)]·pmdta (1a) with [Cp₂MCl₂] (M = Zr, Hf) or [Cp*₂ZrCl₂] in stoichiometric amounts. These compounds were characterized by single crystal X-ray diffraction analyses and, in the case of 2, 3, 5–7, 9, 10 and 12, also by elemental analyses and ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. Exposure of the troticenyl organotin chloride 3 to moisture resulted in its partial hydrolysis and formation of the organostannoxane-bridged bitroticene 4, while palladium-catalyzed Negishi C–C cross-coupling reaction between the troticenylzinc chloride [(η⁷-C₇H₇)Ti(η⁵-C₅H₄ZnCl)] (13) and the iodotroticene 12 or iodobenzene (PhI) led to the fulvalene complexes [(η⁷-C₇H₇)Ti(η⁵-C₅H₄)]₂ (14) and [(η⁷-C₇H₇)Ti(η⁵-C₅H₄Ph)] (15). Compound 4 displays an unsymmetrical structure with the troticenyl fragments cis with respect to the Sn–O–Sn core, whereas compound 14 is centrosymmetrically trans oriented.     

Synthesis and characterization of new difunctional alkynylated (η-arene)(η-cycloocta-1,5-diene)ruthenium(0) complexes as molecular models for organometallic polymers

The new dialkynylated complexes Ru(η⁶-DEB-Si)(η⁴-COD), 4a, Ru(η⁶-DEBP-Si)(η⁴-COD), 4b1, Ru₂(η⁶,η⁶-DEBP)(η⁴-COD)₂, 4b2 [COD = 1,5-cyclooctadiene; DEB-Si = 1,4-bis(trimethylsilylethynyl)benzene; DEBP-Si = 4,4′-bis(trimethylsilylethynyl)biphenyl] have been synthesized by the arene exchange reaction with the complex Ru(η⁶-naphthalene)(η⁴-COD). The complexes Ru(η⁶-DEB)(η⁴-COD), 5a, and Ru(η⁶-DEBP)(η⁴-COD), 5b1, have been prepared by desilylation of the corresponding compounds 4a and 4b1. All the complexes have been fully characterized by means of spectroscopic techniques.     

N-functionalized cyclam based trinuclear copper(II) complexes: electrochemical,magnetic, catalytic and antimicrobial studies

A series of trinuclear Cu(II) complexes have been prepared by Schiff base condensation of 1,8-[bis(3-formyl-2-hydroxy-5-methyl)benzyl]-l,4,8,11-tetraazacyclotetradecane and 1,8-[bis(3-formyl-2-hydroxy-5-bromo)benzyl]-l,4,8,11-tetraazacyclotetradecane with aromatic and aliphatic diamines, Cu(II) perchlorate and triethylamine. The complexes were characterized by elemental and spectroscopic analysis. Electrochemical studies of the complexes in DMF solution show three irreversible one-electron reduction processes around E_pc ¹ = −0.73 to −0.98 V, E_pc ² = −0.91 to −1.20 V and E_pc ³ = −1.21 to −1.33 V. ESR spectra and magnetic moments of the trinuclear Cu(II) complexes show the presence of antiferromagnetic coupling. The rate constants for hydrolysis of 4-nitrophenylphosphate by the Cu(II) complexes are in the range of 3.33 × 10⁻² to 7.58 × 10⁻² min⁻¹. The rate constants for the catecholase activity of the complexes fall in the range of 2.67 × 10⁻² to 7.56 × 10⁻² min⁻¹. All the complexes were screened for antifungal and antibacterial activity.     

Construction of Cd(II)–ferrocenesuccinate coordination complexes via changing adjuvant ligands and anions

Seven Cd(II)–ferrocenesuccinate coordination complexes with the formulas [Cd(η²-FcCOC₂H₄COO)₂(pbbbm)]₂ (1), [Cd(η²-FcCOC₂H₄COO)(pbbbm)Cl]₂ (2), [Cd(η²-FcCOC₂H₄COO)(pbbbm)I]₂ (3), {[Cd(η²-FcCOC₂H₄COO)₂(btx)₂]₂(CH₃OH)_0.5} (4), [Cd(η²-FcCOC₂H₄COO)₂(bix)]₂(H₂O) (5), {[Cd(η²-FcCOC₂H₄COO)(bbbm)_1.5Cl] · (CH₃OH)_0.5}_n (6), and {[Cd(η²-FcCOC₂H₄COO)(mbbbm)Cl] · (H₂O)_2.75}_n (7) [pbbbm = 1,4-Bis(benzimidazole-1-ylmethyl)benzene), btx = 1,4-bis(triazol-1-ylmethyl)benzene), mbbbm = 1,3-bis(benzimidazole-1-ylmethyl)benzene), bix = 1,4-bis(imidazol-1-ylmethyl)benzene, bbbm = 1,1-(1,4-Butanediyl)bis-1H-benzimidazole)] have been synthesized and characterized. Single-crystal X-ray analysis reveals that complexes 1–5 are all dimers and bridged by pbbbm, btx and bix, respectively. But the five complexes present some differences in their dimeric conformations, which can be ascribed to the impacts of adjuvant ligands and counter anions. In contrast to complexes 1–5, both 6 and 7 are of 1-D structures (with the same counter anions), and the former is double ladder-like structure only bridged by bbbm, while the latter is chain-like structure bridged by chlorine anions and adjuvant ligand mbbbm. Notably, various π–π interactions are found in complexes 1–7, and they have significant contributions to molecular self-assembly processes. The electrochemical studies of complexes 1–7 in DMF solution display irreversible redox waves and indicate that the half-wave potentials of the ferrocenyl moieties in these complexes are all shifted to positive potential compared with that of ferrocenesuccinate.     

Synthesis,characterization, and biological and anticancer studies of mixed ligand complexes with Schiff base and 2,2′‐bipyridine

New mixed ligand complexes of transition metals were synthesized from a Schiff base (L¹) obtained by the condensation reaction of oxamide and furfural as primary ligand and 2,2′‐bipyridine (L²) as secondary ligand. The ligands and their metal complexes were studied using various spectroscopic methods. Also thermal analyses were conducted. The mixed ligand complexes were found to have formulae [M(L¹)(L²)]Cl_m ⋅n H₂O (M = Cr(III) and Fe(III): m  = 3, n  = 0; M = Cu(II) and Cd(II): m  = 2, n  = 1; M = Mn(II), Co(II), Ni(II) and Zn(II): m  = 2, n  = 0). The resultant data revealed that the metal complexes have octahedral structure. Also, the mixed ligand complexes are electrolytic. The biological and anticancer activities of the new compounds were tested against breast cancer (MCF‐7) and colon cancer (HCT‐116) cell lines. The results showed high activity for the synthesized compounds.     

Structure and bonding in haloarylgallyl complexes of iron, ruthenium and osmium [(η-C5H5)(CO)2M{Ga(X)(Ph)}]: A theoretical study

Density Functional Theory calculations have been performed for the halophenylgallyl complexes of iron, ruthenium and osmium [(η⁵-C₅H₅)(CO)₂M(Ga(X)Ph)] (M = Fe, Ru, Os; X = Cl, Br, I) at the DFT/BP86/TZ2P/ZORA level of theory. The calculated geometry of iron complexes [(η⁵-C₅H₅)(CO)₂Fe(Ga(Cl)Ph)] and [(η⁵-C₅H₅)(CO)₂Fe(Ga(I)Ph)] is in excellent agreement with structurally characterized complexes [(η⁵-C₅H₅)(CO)₂Fe(Ga(Mes^∗)Cl)], [(η⁵-C₅Me₅)(CO)₂Fe(Ga(Mes^∗)Cl)] and [(η⁵-C₅Me₅)(CO)₂Fe(Ga(Mes)I)] (Mes = C₆H₂Me₃-2,4,6; Mes^∗ = C₆H₂^tBu₃-2,4,6). The M-Ga bond distances as well as Mayer bond order of the M-Ga bonds suggest that the M-Ga bonds in these complexes are nearly M-Ga single bond. The π-bonding component of the total orbital contribution is significantly smaller than that of σ-bonding. Thus, in these complexes the Ga(X)Ph ligand behaves predominantly as a σ-donor. The contributions of the electrostatic interaction terms ΔE_elstat are significantly smaller in all gallyl complexes than the covalent bonding ΔE_orb term. The absolute values of the ΔE_Pauli, ΔE_int and ΔE_elstat contributions to the M-Ga bonds increase in both sets of complexes via the order Fe < Ru < Os. In the complexes [(η⁵-C₅H₅)(Me₃P)₂Fe(Ga(X)Ph)] (X = Cl, Br, I), interaction energy as well as bond dissociation energy decrease upon going from X = Cl to X = I.     

Preparation and reactivity of p-cymene complexes of ruthenium and osmium incorporating 1,3-triazenide ligands

p-Cymene complexes MCl₂(η⁶-p-cymene)L [M = Ru, Os; L = P(OEt)₃, PPh(OEt)₂, (CH₃)₃CNC] were prepared by allowing [MCl(μ-Cl)(η⁶-p-cymene)]₂ to react with phosphites or tert-butyl isocyanide. Treatment of MCl₂(η⁶-p-cymene)L complexes with 1,3-ArNNN(H)Ar triazene and an excess of NEt₃ gave the cationic triazenide derivatives [M(η²-1,3-ArNNNAr)(η⁶-p-cymene)L]BPh₄ (Ar = Ph, p-tolyl). Neutral triazenide complexes MCl(η²-1,3-ArNNNAr)(η⁶-p-cymene) (M = Ru, Os) were also prepared by allowing [MCl(μ-Cl)(η⁶-p-cymene)]₂ to react with 1,3-diaryltriazene in the presence of triethylamine. p-Cymene complexes MCl₂(η⁶-p-cymene)L reacted with equimolar amounts of 1,3-ArNNN(H)Ar triazene to give both triazenide complexes [M(η²-1,3-ArNNNAr)(η⁶-p-cymene)L]BPh₄ and amine derivatives [MCl(ArNH₂)(η⁶-p-cymene)L]BPh₄. A reaction path for the formation of the amine complex is also reported. The complexes were characterised by spectroscopy and X-ray crystallography of RuCl₂(η⁶-p-cymene)[PPh(OEt)₂] and [Ru(η²-1,3-p-tolyl-NNN-p-tolyl)(η⁶-p-cymene){CNC(CH₃)₃}]BPh₄. Selected triazenide complexes were studied as catalysts in the hydrogenation of 2-cyclohexen-1-one and cinnamaldehyde.     

Synthesis,characterization, and cytotoxic and antimicrobial activities of ruthenium(II) arene complexes with N,N-bidentate ligands

Three new complexes, [(η⁶-C₆H₆)RuCl(C₅H₄N-2-CH=N-Ar)]PF₆ (Ar = phenylmethylene (1), (4-methoxyphenyl)methylene (2), and phenylhydrazone (3)), were prepared by reacting [(η⁶-C₆H₆)Ru(μ-Cl)Cl]₂ with N,N′-bidentate ligands in a 1 : 2 ratio. Full characterization of the complexes was accomplished using ¹H and ¹³C NMR, elemental and thermal analyses, UV–vis and IR spectroscopy and single crystal X-ray structures. Single crystal structures confirmed a pseudo-octahedral three-legged, piano-stool geometry around Ru(II), with the ligand coordinated to the ruthenium(II) through two N atoms. The cytotoxicity of the mononuclear complexes was established against three human cancer cell lines and selectivity was also tested against non-cancerous human epithelial kidney (HEK 293) cells. The compounds were selective toward the tumor cells in contrast to the known anti-cancer drug 5-fluoro uracil which was not selective between the tumor cells and non-tumor cells. All the compounds showed moderate activity against MCF7 (human breast adenocarcinoma), but showed low antiproliferative activity against Caco-2 and HepG2. Also, antimicrobial activities of the complexes were tested against a panel of antimicrobial-susceptible and -resistant Gram-negative and Gram-positive bacteria. Of special interest is the anti-mycobacterial activity of all three synthesized complexes against Mycobacterium smegmatis, and bactericidal activity against resistant Enterococcus faecalis and methicillin-resistant Staphylococcus aureus ATCC 43300.     

Synthesis,reactivity and preliminary biological activity of iron(0) complexes with cyclopentadienone and amino‐appended N‐heterocyclic carbene ligands

Neutral and cationic cyclopentadienone (CpO) N‐heterocyclic carbene (NHC) bis‐carbonyl iron(0) complexes bearing, appended to the NHC ligand, either a terminal amino group on the lateral chain, [Fe(η⁴‐CpO)(CO)₂(κC‐NHC(CH₂)_nNH₂)] with n = 2 ( 2a ) and 3 ( 2b ), or a cationic NMe₃⁺ fragment, [Fe(η⁴‐CpO)(CO)₂(κC‐NHC(CH₂)₂NMe₃)](I) ( 3 ), were prepared and characterized in terms of their structure, stability and reactivity. The photochemical properties of 2a and 2b were examined both in organic solvents and in water, revealing the photoactivated release of one CO ligand followed by the formation of the chelated complex [Fe(η⁴‐CpO)(CO)(κ²C,N‐NHC(CH₂)₂NH₂)] ( 4 ), whose molecular structure was confirmed by single crystal X‐ray diffraction studies. This metallacyclization occurs only in the case of 2a , with the ethylene spacer between NHC ring and NH₂ group in the lateral chain, allowing the formation of a stable 6‐membered ring. On the other hand, 2b undergoes decomposition upon irradiation. The reactivity in aqueous solutions revealed the chemical speciation of the complexes at different pH and especially under physiological conditions (phosphate buffer solution at pH 7.4 and 37 °C). The lack of data on the biological properties of iron(0) complexes prompted us to preliminarily investigate their cytotoxicity against model cancer cells (AsPC‐1 and HPAF‐II), along with a determination of their lipophilicity.     

Alkynyl Ti-M complexes based on M(CO)4 and MO2 building blocks (M = Mo, W)

The synthesis and properties of heterobimetallic Ti-M complexes of type {[[Ti](μ-η¹:η²-CCSiMe₃)][M(μ-η¹:η²-CCSiMe₃)(CO)₄]} (M = Mo: 5, [Ti] = (η⁵-C₅H₅)₂Ti; 6, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti; M = W: 7, [Ti] = (η⁵-C₅H₅)₂Ti; 8, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti) and {[Ti](μ-η¹:η²-CCSiMe₃)₂}MO₂ (M = Mo: 13, [Ti] = (η⁵-C₅H₅)₂Ti; 14, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti). M = W: 15, [Ti] = (η⁵-C₅H₅)₂Ti; 16, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti) are reported. Compounds 5-8 were accessible by treatment of [Ti](CCSiMe₃)₂ (1, [Ti] = (η⁵-C₅H₅)₂Ti; 2, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti) with [M(CO)₅(thf)] (3, M = Mo; 4, M = W) or [M(CO)₄(nbd)] (9, M = Mo; 10, M = W; nbd = bicyclo[2.2.1]hepta-2,5-diene), while 13-16 could be obtained either by the subsequent reaction of 1 and 2 with [M(CO)₃(MeCN)₃] (11, M = Mo; 12, M = W) and oxygen, or directly by oxidation of 5-8 with air. A mechanism for the formation of 5-8 is postulated based on the in-situ generation of [Ti](CCSiMe₃)((η²-CCSiMe₃)M(CO)₅), {[Ti](μ-η¹:η²-CCSiMe₃)₂}-M(CO)₄, and [Ti](μ-η¹:η²-CCSiMe₃)((μ-CCSiMe₃)M(CO)₄) as a result of the chelating effect exerted by the bis(alkynyl) titanocene fragment and the steric constraints imposed by the M(CO)₄ entity.The molecular structure of 5 in the solid state were determined by single crystal X-ray diffraction analysis. In doubly alkynyl-bridged 5 the alkynides are bridging the metals Ti and Mo as a σ-donor to one metal and as a π-donor to the other with the [Ti](CCSiMe₃)₂Mo core being planar.