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The first example of intermolecular hydrophosphination of styrene,2 -vinylpyridine and phenylacetylene with PH 3 catalyzed by bis-(amido) complexes [(Me 3 Si) 2 N] 2 M(NHC) 2 (M = Ca, Yb, Sm) coordinated by NHC ligands is described. The reactions of styrene with PH 3 proceed under mild conditions in quantitative yields to afford only anti-Markovnikov product and allow for the chemoselective synthesis of primary,s econdary and tertiary phosphines. Addition of phenylacetylene to PH 3 regardless the initial molar substrates ratio resultsi nt he exclusive formation of at ertiaryt ris-(Z-styryl)-phosphine. Crucial effect of the Lewis base coordinated to the metal ion in precatalyst on catalytic activity in styrene hydrophosphinationw ith PH 3 was demonstrated. Free NHCs were also found to be able to promote addition of PH 3 to styrene, however they provide much lower reactionr ates comparedt ot he metal complexes.The formation of CÀPb onds by single-step intermolecular hydrophosphination reactions of unsaturated substrates is a promising, atom-efficient route to av ariety of phosphorus-containing compounds. To date, an umber of examples of this transformationh ave been achieved due to acid, [1] base, [2] dtransition, [3] alkaline-earth, [4] andr are-earth metal catalysis. [4a, 5] Radicali nitiation [2a,c, 6] was also reported and is covered in several reviews. [2c, 5e, 7] Despite the progress achieved in this area, a substrate scope of this reactionr emains limited and mainly involves activated olefins and ubiquitousp henyl-and diphenylphosphine. Meanwhile, PH 3 addition to alkenes and alkynes, which is ap rogressive and convenient syntheticr oute to av ariety of primary,s econdary and tertiaryp hosphines, still re-mains poorly explored. Ease of synthesis of PH 3 ,i ts low cost (vs. PhPH 2 )a nd availability make it ac ommercially attractive startingc ompound fort he synthesis of phosphines. Hydrophosphination of multiple CÀCb onds with PH 3 becomes feasible under free radical initiation, [8] acid [1] and superbasic [9] conditions, or UV irradiation. [10] However,t his reaction suffers from a lack of selectivity.T he only example of applying late transition metal complexes for catalytic hydrophosphination of activated substrates (acrylonitrile, [11] ethyl acrylate, [12] formaldehyde [13] ) with PH 3 was published by Pringle and co-workers. No examples of PH 3 addition to non-activated olefins, vinyl arenes and alkynes catalyzed by rare-and alkaline-earth metals complexes have been published so far.M oreover,t he examples of hydrophosphination reactions catalyzed by free carbenes also still remain unknown despite the immense progress in organocatalysis achieved through their use. [14] We found that homoand heterolepticY b II ,S m II and Ca II amido complexes [4a,c, 5b] performing with high catalytic activity in styrene hydrophosphination with Ph 2 PH and PhPH 2 proved to be completely inert in the case of PH 3 .C omplex {LO NO4 }YbN(SiMe 3 ) 2 (1) [4a] was the only exception that enabled transformationo fP H 3...

4,4´ Bis(nitramino)azofurazan 2 was obtained by nitration of 4,4 diaminoazofurazan 1. Molecular and crystal structure of nitramine 2 and its ammonium salt 3 were studied by X ray method and quantum chemical calculations at M052X/aug cc pvdz level of theory. Both com pounds adopt ap ap ap conformation. It was shown that the structure of furazan cycle signifi cantly depends on the nature of the substituents at carbon atoms. Crystal structures of 2 and 3 are characterized by sufficiently high density (1.996 and 1.832 g cm -3 at 110K and 1.919 and 1.766 g cm -3 at 295 K, respectively), which is provided, in particular, by strong intermolecular hydrogen bonding and π-π stacking interactions. Among substituted azofurazans and primary nitramines examined by X ray diffraction analysis, 4,4´ bis(nitramino)azofurazan 2 is charac terized by the highest density.

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The cover picture shows the single‐crystal X‐ray structure for C60F18, the first fully characterized aromatic fullerene, possessing a flat and fully delocalized hexagonal benzenoid ring embedded at the center of the fluorinated crown. The bond lengths in this hexagon are all of equal length (1.372 Å). The un‐addended part of the molecule possesses the normal C60 fullerene structure so that the overall appearance is that of a tortoise shell. C60F18 is potentially an important building block for donor–acceptor derivatives with photovoltaic/photonic applications, combining enhanced cage electron withdrawal, with a vacant area for location of donors. The unique geometry also makes the molecule a hexasubstituted benzene, which may be able to participate in η6 coordination to metallic species. Details on this tortoise molecule are described by Slovokhotov, Boltalina, and Taylor et al. on p. 3273 ff.

New chiral P,N-hybrid aryl phosphites have been obtained by one-step phosphorylation of amino and imino alcohols. Complexation of the new ligands with [Rh(CO) 2 Cl] 2 , [Pd(COD)Cl 2 ] and [Pd(allyl)Cl] 2 was found to give chelate complexes [Rh(CO)Cl(η 2 -P ʝ N)], [PdCl 2 (η 2 -P ʝ N)] and [Pd-(allyl)(η 2 -P ʝ N)] + Cl − , respectively. With these new P,N-ligands, up to 82% ee enantioselectivity was achieved in the [a] The new P,N-bidentate aryl phosphites were synthesized by one-step phosphorylation of the corresponding amino and imino alcohols with bis(2,6-dimethylphenyl) chlorophosphite.They divide into two groups: ligands 3aϪ3f, possessing sp 3 -hybridized nitrogen atoms, and ligands 3gϪ3m, which have sp 2 -hybridized nitrogen atoms. All the compounds 3aϪm are soluble in conventional organic solvents and stable under dry conditions for several months. On treatment with [Rh(CO) 2 Cl] 2 , their neutral carbonyl(chloro)Rh I complexes were obtained.The ν(CO) and 1 J P,Rh parameters in their IR and 31 P NMR spectra act as sensitive indicators, which characterise the mode of complexation of the P,N-ligands and allow the π-acceptor ability of the phosphorus centre and the degree of electronic non-symmetry of the ligands to be estimated. [13Ϫ15] In general, ligands 3aϪ3m give chelate complexes. Thus, the

We report the synthesis, structures, magnetic and luminescent properties of a series of three-blade propeller homoleptic lanthanide complexes [LnL3](ClO4)3·H2O·2MeCN (Ln = Eu (1), Tb (2), Dy (3), Er (4), Yb...