Solid scheme

Reactions of solids. Scheme of reaction pathways indicating relationships with kinetic characteristics... 

Figure 3. Measured (dotted) and calculated CPs of Si by the FLAPW-LDA (dashed) and the FLAPW-SIC (solid) schemes, The theoretical core profile is represented by a dash-dotted curve (after Kubo et al. [10]). 

Recently, we succeeded in the synthesis and structural characterization of first niobium-containing metallasilsesquioxane complex. In analogy to the corresponding reactions with titanium tetraalkoxides, niobium pentaethoxide cleanly reacts with 3 in a 1 1 molar ratio to give high yields of dimeric [Cy7Si70i2Nb0Et( U-OEt)]2 (149) as a colorless, crystalline solid (Scheme 49). 

A great advantage of this method is the synthesis of bis(l,2,3-dithiazoles) from diaminodithiols (1997JA12136, 1999CM164, 2000JA7602). Reduction of radical cations formed with PhsSb led to neutral heterocycles 122 and 123 as air-stable crystalline solids (Scheme 61). 

Ammonia and pyridine are frequently used as probe molecules for the characterization of acidic surfaces, but they also adsorb on strongly basic sites. Tsyganenko et al. (54) proposed various species resulting from NH3 adsorption on basic solids (Scheme 1). The formation of species I corresponds to hydrogen bonding to a basic surface oxygen, and species II, formed by dissociation to give NH2 and hydroxyl species, involves an acid-base site. Such adsorption requires... 

Note also the reactivity of the heteroleptic plumbylene 174 toward carbon disulfide. Treatment of 174 with excess amount of carbon disulfide resulted in a formation of unexpected product, lead(II) bis(aryl trithiocarbonate) (192), as a yellow, air- and moisture-stable solid (Scheme 14.85). The reaction must involve not only the insertion of carbon disulfide into the Pb—S bond, but also the formal insertion of a sulfur atom into the Pb C(Tbt) bond and subsequent insertion of another... 

The reaction of excess tellurium tetrachloride with LiCHPhC(CF3)2OLi at — 78 °C and further warming of the reaction mixture to room temperature affords the spirotellurane 21 in 13% yield as an air-stable solid (Scheme 17) <2002TL6775>. 

The addition of the S=0 bond across the C=S bond took part in the reaction of sulfur trioxide with methylidene sulfur tetrafluoride <1995HAC611>. The resulting 1,2,4-oxadithietane 16 was isolated as a stable colorless solid (Scheme 35). 

G. M. J. Schmidt, with his ground-breaking work on the solid-state reactions of cinnamic acids, was one of the first to look at intermediate stages of a reacting organic solid (Scheme 17) [63,108,109]. He did this, in the early 1960s, with the... 

A variety of other poly-furans have been employed in Wittig reactions as either the aldehyde or the ylide component. Condensation of 5,5 -thiodi-2-furaldehyde (176), for instance, with the 2,2 -bifuryl-5,5 -diylbis-(methylenetriphenyl-phospho-nium bromide) (177) under basic conditions, gave the macrocycle 178 as orange crystals in 1.3% yield (Scheme 29) [148]. Two macrocyclic annulenones 182 and 184 were also obtained [149] from the base induced condensation of 181 with the dialdehydes 180 or 183, respectively. Both products are obtained in moderate yields (12-15%) and are highly colored solids (Schemes 30 and 31, respectively). 

After coupling of (hetero)aroyl chlorides 7 and terminal alkynes 4, hydrazines 29, and acetic acid are added and reacted in the same reaction vessel. Best results for the formation of pyrazoles 30 are obtained by dielectric heating in the micro-wave oven at 150°C for 10 min in the presence of methanol. Pyrazoles 30 are obtained in good to excellent yields, predominantly as colorless crystalline solids (Scheme 21) [113]. This concept has also been applied to the nonregioselective synthesis of 3,5-disubstituted pyrazoles 30 (R = H) upon conductive heating in the cyclocondensation step [114]. 

A similar approach using bis(chlorozinc)polyphenylene reagents has yielded a series of phenylene-bridged bisferracarboranes, isolated as yellow air-stable solids (Scheme 4).12 An X-ray crystallographic study on the triphenylene complex 19 Scheme 4 b=bh,b... 

An alternative synthesis of the tungsten bis-silanol A starts with the regioselective chlorination of the metal-bound Si-H function of 6 with PdCli. The corresponding tungsten chlorosilane 9 is isolated in 85% yield as a yellow solid (Scheme 2). 

The Ni-catalyzed cross-coupling reaction of alkynyl Grignard reagents (21) with /ra/jj-dichlo-roethylene (22) has been applied to a simple procedure for the preparation of the protected form (23) of an extremely unstable synthon, hexadiynene (24). Separation of the diastereomers (23a from 23b) is facile since the former is an oil and the latter is a solid (Scheme 10). ... 

The synthesis and characterization of enantiomerically pure ansa-cyclopentadienyl organolanthanides Me2Si(ButCp)[(+)- i o-Men-Cp]Ln(CH(SiMe3)2 and their use as precatalysts for asymmetric olefin hydrogenation have been reported. In a one-pot reaction starting from 6,6-dimethylfulvene, methyllithium, and dimethyldichloro-silane the desired product Me2Si(ButCp)Cl was obtained, which was alkylated with Na[(+)-row-Men-Cp] to afford the neutral ligand. Reaction with BunLi afforded the dilithium salt as a colorless crystalline solid (Scheme 161). 

When 2,2 -dianiinobiphenyl is bis-diazotized at 0°C (see also Section II,A,2) and the solution is neutralized with ammonia at that temperature, dibenzo[rf,/][l,2,3]triazepine (22) precipitates as a yellow solid (Scheme 4). Although moderately stable, 22 rearranges quantitatively to benzo[c]-cinnoline-5-imide (23) on heating in benzene. The imide (23) is also the... 

In contrast, the adduct (41) obtained from singlet oxygen and l,4-diphenyl-3/7-2-benzopyran-3-one (40) is a stable, crystalline solid (Scheme 2) <78JA2564>. Nonetheless, (41) decomposes in boiling benzene giving o-dibenzoylbenzene (43) and phenyl o-benzoylbenzoate (45) in 85% and 5% yield respectively. No luminescence is detected. The major reaction course is decarboxylation to the intermediate o-xylylene peroxide (42), which can be trapped as its Diels-Alder adduct with maleic anhydride. The ester (45) could have arisen directly from (41) by decarbonylation and concomitant... 

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