Synthesis and Characterization of a Rhenanaphthalene Isomer.

Exploration of organometallic metallacycles has led to the development of various polycyclic compounds with fascinating structures, which could be used as functional materials. In this work, a new rhenanaphthalene isomer was isolated from the reaction of ReH (PMe Ph) with o-ethynylphenyl alkyne in the presence of excess HCl. Its structure was then identified using the single-crystal X-ray diffraction and NMR spectroscopy.

Aromatic chloroosmacyclopentatrienes.

Aromatic metallacycles are of considerable current interest. Reported aromatic metallacycles are mainly those with carbon, nitrogen, oxygen and sulfur. In this work, we report the synthesis and characterization of aromatic chloroosmacyclopentatrienes, which represent the first structurally confirmed metallaaromatic with a chlorine atom in its framework.

Synthesis, Characterization and Electronic Structure of Dirhenadehyro[12]annulene Complexes.

Treatment of the SiMe -protected dichloro-rhenium carbyne complexes Re{≡CCH=C(R)C≡CSiMe }Cl (PMe Ph) (R = CMe , 1-adamantyl) with CsF in methanol directly afforded the 12-membered metallacycles {ReCl(PMe Ph) } {≡CCH=C(R)C≡C-} . The electronic structure of the metallacycle was investigated by density functional calculations. The UV-vis spectrum of the metallacycle shows a red-shifted band compared to that of the starting dichlorocarbyne complex.

Synthesis and characterization of metallapentalenoxazetes by the [2+2] cycloaddition of metallapentalynes with nitrosoarenes.

Cycloaddition reactions of carbynes in metallacycles with π-bond substrates have been rarely reported. We report the first [2+2] cycloaddition of metallapentalynes with nitrosoarenes to obtain the first metallapentalenoxazetes, and their photophysical and electrochemical properties were studied by UV-Vis spectroscopy and cyclic voltammetry with the help of theoretical calculations.

Synthesis and Characterization of Cyclopropaosmanaphthalenes Containing a Fused σ-Aromatic Metallacyclopropene Unit.

Metalla-aromatics are important complexes that show unique properties owing to their highly conjugated systems, which show Hückel or Möbius aromaticity. Recently, several metalla-aromatics showing spiro-aromaticity or σ-aromaticity have been reported. Herein, we report the isolation of the first cyclopropametallanaphthalenes, in which the metallacyclopropene ring shows σ-aromaticity and weak hyperconjugative aromaticity.

Synthesis, characterization and electrochemical properties of stable osmabenzenes containing PPh3 substituents.

Treatment of [OsCl(2)(PPh(3))(3)] with HC[triple bond]CCH(OH)C[triple bond]CH/PPh(3) produces the osmabenzene [Os{CHC(PPh(3))CHC(PPh(3))CH}Cl(2)(PPh(3))(2)][OH] (2), which is air stable in both solution and solid state. The key intermediate of the one-pot reaction, [OsCl(2){CH=C(PPh(3))CH(OH)C[triple bond]CH}(PPh(3))(2)] (3), and the related complex [Os(NCS)(2){CHC(PPh(3))CH(OH)C[triple bond]CH}(PPh(3))(2)] (7) have been isolated and characterized, further supporting the proposed mechanisms for the reaction. Reactions of 3 with PPh(3), NaI, and NaSCN give osmabenzene 2, iodo-substituted osmabenzene [Os{CHC(PPh(3))CHCICH}I(2)(PPh(3))(2)] (4), and thiocyanato-substituted osmabenzene [Os{CHC(PPh(3))CHC(SCN)CH}(NCS)(2)(PPh(3))(2)] (5) respectively.

Osmabenzenes from the reactions of HC[triple bond]CCH(OH)C[triple bond]CH with OsX2(PPh3)3 (X = Cl, Br).

Treatment of OsX2(PPh3)3 (X = Cl, Br) with HCCCH(OH)CCH in THF produces OsX2(CH=C(PPh3)CH(OH)CCH)(PPh3)2, which reacts with PPh3 to give osmabenzenes [Os(CHC(PPh3)CHC(PPh3)CH)X2(PPh3)2]+.