The extra-large-pore germanosilicates with UTL topology have been synthesized using a large variety of spiroazocompounds as structure-directing agents. Synthesis conditions were optimized and zeolites with a high crystallinity degree were obtained with 13 different organic structure-directing agents. The influence of the composition of the reaction mixture and template nature (structure, hydrophilicity/hydrophobicity balance, rigidity, pK a) on the phase selectivity, crystallinity degree, and adsorption properties of zeolites with UTL structure was investigated. Selection criteria of organic molecules as potential structure-directing agents (SDAs) in the synthesis of large-pore and extra-large-pore zeolites from silicate and germanosilicate media are proposed. The optimum synthesis time was determined to be 4−9 days for different SDA and (Si + Ge)/SDA molar ratios. Clear synergism between the optimum structure of organic template and the presence of critical amount of inorganic component (GeO2) was evidenced. The UTL zeolite crystallizes as tiny sheets ∼10 μm thick. The effect of the organic template on the size and shape of the crystals was found. The micropore volume of the best crystals is 0.22−0.24 cm3/g, with a micropore diameter of 1.05 nm, based on density functional theory (DFT), and Saito−Foley analyses of adsorption isotherms.

Hydrogen sulfide reacts with tucked-in titanocene complexes [Ti(III){η 5 :η 1 -C 5 Me 4 (CH 2 )}Cp*] (Cp* = η 5 -C 5 Me 5 ) (2) and [Ti{η 4 :η 3 -C 5 Me 3 (CH 2 ) 2 }Cp*] (3) and their precursors [Cp* 2 TiMe] (2a) and [Cp* 2 Ti(η 2 -Me 3 SiCtCSiMe 3 )] (3a), respectively, to give the corresponding titanocene hydrosulfides [Cp* 2 Ti(SH)] ( 4) and [Cp* 2 Ti(SH) 2 ] (1), respectively. Hydrogen sulfide also cleaves intramolecular σor π-Ti-C bonds in ansa-[Ti III (η 1 :η 5 :η 5 -C 5 Me 4 SiMe 2 CHCH 2 SiMe 2 C 5 Me 4 )] ( 5) and ansa-[Ti II (η 2 :η 5 :η 5 -C 5 Me 4 SiMe 2 CHdCHSiMe 2 C 5 Me 4 )] ( 6), affording hydrosulfides ansa-[(η 5 -CH 2 Me 2 SiC 5 Me 4 ) 2 Ti(SH)] ( 7) and ansa-[(η 5 -CH 2 Me 2 SiC 5 Me 4 ) 2 Ti(SH) 2 ] (8). The S-H bonds of hydrosulfides 4 and 7 were able to react with the Ti-C bonds in 2 and 5, affording titanocene sulfides [(Cp* 2 Ti III ) 2 S] (11) and ansa-[{(η 5 -CH 2 Me 2 SiC 5 Me 4 ) 2 Ti III } 2 S] (12), respectively. Combination of 7 with 2a gave rise to the mixed titanocene sulfide [ansa-{(η 5 -CH 2 SiMe 2 C 5 Me 4 ) 2 Ti}S(TiCp* 2 )] ( 13). The titanium(III) d 1 electrons in 11-13 form an electronic triplet state well observable by EPR spectra in toluene glass. All the hydrosulfides were decomposed by sunlight. Compound 1 eliminated Cp*H and H 2 S, while 4 mainly Cp*H. Apparently formed transient [Cp*TiS] species probably gave rise to the serendipitously isolated cluster [{Cp*Ti(S)} 4 ] (14). Crystal structures of the all complexes were determined by X-ray diffraction analysis.

The presence of a trimethylsilyl substituent in place of one of the methyl groups of each of the cyclopentadienyl ligands of decamethyltitanocene enhances the thermal stability of the resulting complex, [Ti II {η 5 -C 5 Me 4 (SiMe 3 )} 2 ] (1), and controls the products formed in thermolysis of its methyl derivatives. Titanocene 1 was found to be stable in toluene solution up to 90 °C, while under vacuum at 140 °C it liberated hydrogen to give the asymmetrical doubly tucked-in titanocene [Ti II {η 3 :η 4 -C 5 Me 2 (SiMe 3 )(CH 2 ) 2 }-{η 5 -C 5 Me 4 (SiMe 3 )}] (3). The mono-and dimethyl derivatives of 1, the complexes [Ti III Me{η 5 -C 5 Me 4 -(SiMe 3 )} 2 ] (5) and [Ti IV Me 2 {η 5 -C 5 Me 4 (SiMe 3 )} 2 ] (6), undergo thermolysis at lower temperature than do the corresponding permethyltitanocene derivatives and eliminate hydrogen from their trimethylsilyl group. Thus, the known [Ti III {η 5 :η 1 -C 5 Me 4 (SiMe 2 CH 2 )}{η 5 -C 5 Me 4 (SiMe 3 )}] (4) was obtained from 5, and compound 6 afforded [Ti II {η 6 :η 1 -C 5 Me 3 (CH 2 )(SiMe 2 CH 2 )}{η 5 -C 5 Me 4 (SiMe 3 )}] (7) at only 90 °C, both with liberation of methane. Crystal structures of 3, 5, and 7 were determined. DFT calculations for titanocene 1 revealed that the metal-cyclopentadienyl bonding is accomplished via a three-centerfour-electron orbital interaction. An auxiliary long-range Si-C bond interaction with the Ti center was also established, providing a reason for the enhanced thermal stability of 1. The molecular orbitals participating in the exo methylene-titanium bonds for 3 and 7 are also three-centered and are compatible with the assignment of their activated ligands to η 3 :η 4 -allyldiene and η 6 -fulvene structures, respectively. Qualitatively, the much higher thermal stability of 3 and 7 compared to that of 1 is due to the exploitation of four d orbitals in the bonding molecular orbitals for 3 and 7 versus only two d orbitals for 1.

Ethene complexes of titanocenes [Ti(II)(η 2 -C 2 H 4 )(Cp′) 2 ] for Cp′ = η 5 -C 5 Me 5 (1), η 5 -C 5 Me 4 t-Bu (2), η 5 -C 5 Me 4 SiMe 3 (3), and η 5 -C 5 HMe 4 (4) were prepared by reduction of corresponding titanocene dichlorides with magnesium in THF in the presence of ethene. Thermolysis of 1−3 in toluene solution at a maximum of 100 °C resulted in elimination of ethane, affording cleanly doubly tucked-in titanocene compounds 5−7, respectively. Experiments with 2 and 3 in NMR tubes proved that symmetrical isomers 6a and 7a were formed first, and these thermally isomerized to thermodynamically more stable asymmetrical isomers 6b and 7b. The energy difference between 7a and 7b calculated by DFT methods was 15.3 kJ/mol. Thermolysis of 4 in m-xylene required a temperature of 135 °C, affording a mixture of 8b > 8a and "dimeric dehydro-titanocene" 9 as a concurrent product of hydrogen abstraction. In contrast to thermolysis in solvents, heating of 1 and 2 in high vacuum to 135 °C resulted in sublimation of known titanocenes [Ti(C 5 Me 5 ) 2 ] (10) and [Ti(η 5 -C 5 Me 4 t-Bu) 2 ] (13) (Chirik et al. J. Am. Chem. Soc. 2004, 126, 14688−14689), respectively. The former isomerized in hexane solution to the tucked-in hydride [TiH{C 5 Me 4 (CH 2 )}(C 5 Me 5 )] (10A) as described by Bercaw (J. Am. Chem. Soc. 2004, 126, 14688−14689). A mixture of 10/ 10A decayed within days to give major paramagnetic products [TiH(C 5 Me 5 ) 2 ] (11) and singly tucked-in titanocene [Ti{C 5 Me 4 (CH 2 )}(C 5 Me 5 )] ( 12) and minor diamagnetic 5 and its so far unknown, less stable isomer [Ti{C 5 Me 4 (CH 2 )} 2 ] (10B), identified by NMR spectra and corroborated by DFT calculations. Solid 3 eliminated ethene at only 80 °C, leaving titanocene 14, whereas compound 4 sublimed at 135 °C mostly without decomposition. Cocrystals of 10 with [TiCl(C 5 Me 5 ) 2 ] (1:2) (10C) afforded an X-ray single-crystal structure with linear geometry for 10. The ethene complexes 1−4 differed in their reactivity toward but-2-yne: compounds 1 and 4 yielded the respective [Ti(IV)(η 1 : η 1 -CH 2 CH 2 CMeCMe)(Cp′) 2 ] 2,3dimethyltitanacyclopent-2-ene complexes 15 and 16, whereas 2 and 3 replaced ethene with but-2-yne, affording the [Ti(II)(η 2 -MeCCMe)(Cp′) 2 ] complexes 17 and 18, respectively. Crystal structures of 2, 4, 10C, 15, 17, and 18 have been determined by X-ray crystallography.

Ruthenium tetrazene complexes with general formula [Cp*RuCl(1,4-R 2 N 4)] (Cp* = η 5-C 5 Me 5), where R = benzyl (1), 2-fluorobenzyl (2), β-D-glucopyr anosyl-unprotected (3a) and acyl-protected (3b-d), 2-acetamido-β-Dglucopyranosyl-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 ionizationmass 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). K E Y W O R D S anticancer activity, glucose derivatives, ruthenium complexes, tetrazene ligands V. Hamala and A. Martišová contributed equally to this study.

The singly tucked-in permethyltitanocene 1 reacts with an excess of internal alkynes to give the 1:1 adducts 3a−c,f−i, arising from insertion of the alkyne triple bond into the titanium−methylene bond. Only the simplest species, 2-butyne, inserted two molecules to give the known compound 2; however, at a 1:1 stoichiometric ratio the 1:1 adduct 3j was also smoothly formed. 1,4-Disubstituted conjugated diynes with CMe3 or SiMe3 substituents reacted in the same way by only one triple bond to give 3d,e, respectively. The dimethylsilylene-bridged dialkynes Me2Si(CCR)2 (R = SiMe3, CMe3) afforded compounds 3k,l with both triple bonds reacting. After insertion of the first triple bond, the second one underwent a rearrangement which resulted in substituent shift and formation of a silacyclobutene ring linked to the titanium atom. Alkynes bearing the bulky substituents CMe3 and SiMe3 were unreactive. Among a number of olefins and 1,3-butadiene, only ethene reacted to give cleanly the 1:1 adduct 3m. The structures of the paramagnetic [TiIII(η5-C5Me5){η5:η1-C5Me4(CH2CR1CR2)}] products 3a−g,k,l were determined by single-crystal X-ray diffraction analysis. These compounds and compounds 3h−j,m, whose crystal structures could not be determined, were chlorinated with PbCl2 to give the diamagnetic products [TiIVCl(η5-C5Me5){η5:η1-C5Me4(CH2CR1CR2)}] (4a−j) and the corresponding chlorotitanocene derivatives 4k−m. The solution structures of 4a−m were determined by 1H and 13C NMR spectroscopy, and crystal structures for 4b,e,g,l,m were found by single crystal X-ray diffraction analysis. DFT calculations threw light on the transition-state molecule for the formation of 3j and revealed a steric hindrance to be responsible for preventing the insertion of a second molecule of hex-3-yne, the closest homologue of but-2-yne, to react with 3i, forming a homologue of 2.

Bis(decamethyltitanocene) oxide, [(Cp* 2 Ti) 2 O] (1; Cp* = η 5 -C 5 Me 5 ) has been obtained as a yellow crystalline solid after reacting equimolar amounts of the hydride [Cp* 2 TiH] and the hydroxide [Cp* 2 Ti(OH)]. The solid-state structure of 1 revealed a linear Ti−O−Ti arrangement and a mutual, nearly perpendicular orientation of the bent-sandwich titanocene moieties; the length of both Ti−O bonds amounted to 1.9080(3) Å. A unique structural feature was a close-to-eclipsed conformation of the cyclopentadienyl ligands, attributed to the high steric congestion of 1. The molecule in toluene glass exhibited a triplet state EPR spectrum of rhombic symmetry, having zero field splitting D = 0.02159 cm −1 and E = 0.00230 cm −1 . The 1 H NMR spectrum of 1 in toluene-d 8 displays a paramagnetic resonance at δ 4.3 ppm (Δν 1/2 ≈ 270 Hz). Compound 1 reacts with 1 molar equiv of water to give [Cp* 2 Ti(OH)]. In CD 2 Cl 2 , 1 is oxidized to yield the major product [(Cp*TiCl 2 ) 2 O] and minor product [{Cp*Ti(Cl)O} 3 ].

Cationic group 4 metallocene complexes with pendant imine and pyridine donor groups were prepared as stable crystalline [B­(C6F5)4]− salts either by protonation of the intramolecularly bound ketimide moiety in neutral complexes [(η5-C5Me5)­{η5-C5H4CMe2CMe2C­(R)N-κN}­MCl] (M = Ti, Zr, Hf; R = t-Bu, Ph) by PhNMe2H+[B­(C6F5)4]− to give [(η5-C5Me5)­{η5-C5H4CMe2CMe2C­(R)NH-κN}­MCl]+[B­(C6F5)4]− or by chloride ligand abstraction from the complexes [(η5-C5Me5)­(η5-C5H4CMe2CH2C5H4N)­MCl2] (M = Ti, Zr) by Li­[B­(C6F5)4]·2.5Et2O to give [(η5-C5Me5)­(η5-C5H4CMe2CH2C5H4N-κN)­MCl]+[B­(C6F5)4]−. Solid state structures of the new compounds were established by X-ray diffraction analysis, and their electrochemical behavior was studied by cyclic voltammetry. The cationic complexes of Zr and Hf, compared to the corresponding neutral species, exhibited significantly enhanced luminescence predominantly from triplet ligand-to-metal (3LMCT) excited states with lifetimes up to 62 μs and quantum yields up to 58% in the solid state. DFT calculations were performed to explain the structural features and optical and electrochemical properties of the complexes.