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

Abstract

Treatment of the SiMe3‐protected dichloro‐rhenium carbyne complexes Re{≡CCH=C(R)C≡CSiMe3}Cl2(PMe2Ph)3 (R = CMe3, 1‐adamantyl) with CsF in methanol directly afforded the 12‐membered metallacycles {ReCl(PMe2Ph)3}2{≡CCH=C(R)C≡C−}2. 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. Treatment of {ReCl(PMe2Ph)3}2{≡CCH=C(CMe3)C≡C−}2 with HCl produced the dichloro‐rhenium carbyne complex Re{≡CCH=C(CMe3)C≡CH}Cl2(PMe2Ph)3, which is consistent with the electronic structure of the 12‐membered metallacycles.

Synthesis and characterization of rhena[10]annulynes

“…3). The Re1–C1 bond length (1.748(10) Å) is within the range of those reported for the ReC bonds (1.672–1.851 Å), 10 g ,15,17 and is slightly shorter than that of 3a (1.7648(19) Å). The Re1–C9 bond length of (1.868(13) Å) is within the lower range of typical ReCC bonds (1.840–2.046 Å).…”

“…The Re1–C1 bond length of 1.7670(19) Å is within the range of those reported for typical ReC bonds (1.672–1.851 Å). 10 g ,15,17 The Re1–C1–C2 angle (172.45(16)°) is close to 180°. The structural parameters are similar to those of the reported rhenium carbyne complexes.…”

“…Metallacycles with larger ring systems are mainly limited to dimetallic cycles, such as dimetalla[10]annulenes ( VII ), 14 and dimetalladehydro[12]annulenes ( VIII ). 15…”

1D Coordination π–d Conjugated Polymers with Distinct Structures Defined by the Choice of the Transition Metal: Towards a New Class of Antiaromatic Macrocycles

“…A combined experimental and theoretical study allowed us to resolve its chemical structure consisting of a 12‐membered ring incorporating two copper centers. These macrocycles can be considered as a new class of antiaromatic compounds [45, 46] …”

“…Ac ombined experimental and theoretical study allowed us to resolve its chemical structure consisting of a1 2-membered ring incorporating two copper centers.T hese macrocycles can be considered as anew class of antiaromatic compounds. [45,46] Results and Discussion Them etals Cr,F e, Co and Ni are introduced as neutral metal atoms from an electron-beam evaporator while Cu is provided directly by the Cu substrate (as detailed in the Supplementary Information). Theligand precursor 2HQDI is deposited simultaneously by sublimation, and is let to react on Cu(111) and Au(111) surfaces with the metal atoms.W ith all metals,i solated 1D metal-organic coordination polymers are obtained.…”