Multiple Bonds between Transition Metals and “Bare” Main Group Elements: Links between Inorganic Solid State Chemistry and Organometallic Chemistry

The last two decades have seen a dramatic development in the study of metal-metal multiple bonds, particular successes being recorded in the field of organometallic chemistry. Syntheses designed to produce novel transition metal complexes with single, double, triple and quadruple metal-metal bonds occupy a most important place in such research, as also do reactivity studies. A striving to establish general principles has provided much of the motivation for such work, but one less obvious goal—the commercial application of the catalytic properties of metal-metal multiple bonding systems, in the medium and long term—should not be overlooked. All aspects of the investigations of metal-metal multiple bonds also apply to a particular class of compound that has, however, enjoyed little lime-light and thus deserves the present review: complexes with multiple bonds between transition metals and substituent-free (“bare”) main group elements. Although based mostly on accidental discoveries, the few noteworthy examples are now beginning to unfold general concepts of synthesis that are capable of being extended and thus are deserving of exploitation in preparative chemistry. The availability of further structural patterns exhibiting multiple bonds between transition metals and ligand-free main group elements might enable preparative organometallic chemistry to expand in a completely new direction (for instance by the stabilizing or activation of small molecules at the metal complex). This essay discusses the chemistry of complexes of bare carbon, nitrogen, and oxygen ligands (carbido-, nitrido-, and oxo-complexes) and their relationships to higher homologues from both a synthetic and a structural point of view.     

Erprobte Verfahren zur Ultramikro-Elementaranalyse

Zusammenfassung Es wird über ein allgemein anwendbares Verfahren zur CH-Bestimmung mit Einwaagen von 0,4–1 mg berichtet. Die Verbrennung erfolgt in einer verkleinerten Pregl-Apparatur, wobei als Verbrennungs- und Treibgas Helium mit 5–10% Sauerstoff dient. Wasser und Kohlendioxid werden aus dem Gasstrom ausgefroren, in einer evakuierten zweiteiligen Meßapparatur fraktioniert umkondensiert und dort über ihre Drucke bestimmt.

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Summary A generally applicable method is described for the determination of carbon and hydrogen with sample weights of 0.4 to 1 mg. The combustion is carried out in a very small, modified Pregl-apparatus, employing helium containing 5–10% oxygen as combustion and entraining gas. Water and carbon dioxide are removed from the gas stream by freezing. Then water and carbon dioxide are evaporated and fractional-condensed in a vacuum apparatus, where their quantities are determined by their pressures.

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Die Versuche wurden außerordentlich sorgfältig von Herrn Nicklas durchgeführt.     

Structure and synthesis of leucettidine

The structure of leucettidine ($\text{1}$$\text{2}$) has been revised according to its UV-data to 6-(1-hydroxypropyl)-1-methyllumazine and has been proven by an unambiguous synthesis of this natural product.     

Diastereo- and Enantiocontrolled Synthesis of (–)-Allosedamine via Cycloaddition of a Chiral Nitrone

The piperidine alkaloid (–)-allosedamine ( 1 ) has been synthesized, in 21% overall yield, in nine steps starting from the formyl-ester 4 . The synthesis features the reaction cascade 7 → 3 → 2 , involving asymmetric electrophilic enolate hydroxyamination, hydroxylamine/aldehyde condensation, and nitrone/styrene cycloaddition, as well as the reductive N/O cleavage-decyanation 12 → 1 .     

Reduction of 1,4-dichlorobut-2-yne by titanocene to a 1,2,3-butatriene. Formation of a 1-titanacyclopent-3-yne and a 2,5-dititanabicyclo[2.2.0]hex-1(4)-ene

The 2,5-dititanabicyclo[2.2.0]hex-1(4)-ene (bis-titanocene-mu-(Z)-1,2,3-butatriene complex)3 is formed starting from [Cp2Ti(eta2-Me3SiC2SiMe3)] by in situ generated titanocene and 1,4-dichlorobut-2-yne via the 1-titanacyclobut-3-yne (2).     

Microwave-assisted synthesis of 1-aryl-3-acetyl-1,4,5,6-tetrahydrobenzimidazo[1,2-d][1,2,4]triazine: first example of a novel ring system

Novel highly functionalized benzimidazoles were synthesized in two steps by microwave irradiation: construction of the benzimidazole ring followed by ring closure to the new tricyclic system.     

The weakly bound He-HCCCN complex: high-resolution microwave spectra and intermolecular potential-energy surface

Rotational spectra of the weakly bound He-HCCCN and He-DCCCN van der Waals complexes were observed using a pulsed-nozzle Fourier-transform microwave spectrometer in the 7-26-GHz frequency region. Nuclear quadrupole hyperfine structures due to the 14N and D nuclei (both with nuclear-spin quantum number I = 1) were resolved and assigned. Both strong a and weaker b-type transitions were observed and the assigned transitions were used to fit the parameters of a distortable asymmetric rotor model. The dimers are floppy, near T-shaped complexes. Three intermolecular potential-energy surfaces were calculated using the coupled-cluster method with single and double excitations and noniterative inclusion of triple excitations. Bound-state rotational energy levels supported by these surfaces were determined. The quality of the potential-energy surfaces was assessed by comparing the experimental and calculated transition frequencies and also the corresponding spectroscopic parameters. Simple scaling of the surfaces improved both the transition frequencies and spectroscopic constants. Five other recently reported surfaces [O. Akin-Ojo, R. Bukowski, and K. Szalewicz, J. Chem. Phys. 119, 8379 (2003)], calculated using a variety of methods, and their agreement with spectroscopic properties of He-HCCCN are discussed.     

MM3 parametrization of four‐ and five‐coordinated rhenium complexes by a genetic algorithm—Which factors influence the optimization performance?

Genetic algorithms (GA) were used to solve one of the multidimensional problems in computational chemistry, the optimization of force field parameters. The correlation between the composition of the GA, its parameters (p(c), p(m)) and the quality of the results were investigated. The composition was studied for all combinations of a Simple GA/Steady State GA with a Roulette Wheel/Tournament Selector using different values each for crossover (0.5, 0.7, 0.9) and mutation rates (0.01, 0.02, 0.05, 0.10, 0.20). The results show that the performance is strongly dependent on the GA scheme, where the Simple GA/Tournament Selector yields the best results. Two new MM3 parameters were introduced for rhenium compounds with coordination number four (204) and coordination number five (205), the formal oxidation states of rhenium ranging from +V to +VII. A manifold of parameters (Re-C, N, O, S) was obtained by using a diverse set of CSD structures. The advantage of the GA vs. UFF calculations is shown by comparison of several examples. The GA optimized parameters were able to reproduce the geometrical data of the X-ray structures.     

Nucleotides. Part XLIV. Synthesis,characterization, and biological activity of monomeric and trimeric cordycepin-cholesterol conjugates and inhibition of HIV-1 replication

The antivirally active 3′-deoxyadenylyl-(2′–5′)-3′-deoxyadenylyl-(2′–5′)-3′-deoxyadenosine (cordycepin trimer core) was modified at the 2′- or 5′-terminus, by attachment of cholesterol via a carbonate bond (→ 15 ) or a succinate linker (→ 16 and 27 ) to improve cell permeability. The corresponding monomeric conjugates 4 , 7 , and 21 of cordycepin were prepared as model substances to study the applicability of the anticipated protecting groups – the monomethoxytrityl (MeOTr), the (tert-butyl)dimethylsilyl (tbds), and the β -eliminating 2-(4-nitrophenyl)ethyl (npe) and 2-(4-nitrophenyl)ethoxycarbonyl (npeoc) groups – for the final deblocking steps without harming the ester bonds of the conjugate trimers. The syntheses were performed in solution using phosphoramidite chemistry. The fully protected trimer conjugates 13 , 14 , and 26 as well as all intermediates were characterized by elemental analyses, UV and ¹H-NMR spectra. The deblocked conjugates 15 , 16 , and 27 were pure according to HPLC and showed the correct compositions by mass spectra. Comparative biological studies indicated that cordycepincholesterol conjugate trimers 16 and 27 were 333- and 1000-fold, respectively, more potent inhibitors of HIV-1-induced syncytia formation than cordycepin trimer core.     

The fluoride ion-selective electrode in flow injection analysis: Part 1. General Methodology

A simple flow-injection system for determination of traces of fluoride by means of the fluoride-selective electrode is presented. A comparison of several flow-cell arrangements confirmed the advantages of a well-jet design. Systematic investigations of the parameters affecting response times (i.e., polishing procedure, flow rate, carrier composition) established the optimal experimental conditions for measurements down to 1 μg l^?1 fluoride. Calibration plots in the lower μg l^?1 range were neither Nernstein nor linear, but good precision (0.5–5%) was obtained even when the potential differences for concentration steps of one decade were as small as 3 mV.