We report herein the first example of the conversion of metallabenzyne II and isometallabenzene III. The osmium hydride vinylidene complex 1 reacts with HC≡CCH(OEt)(2) to give osmabenzyne 3 via isoosmabenzene 2. Compound 3 exhibits high thermal stability in air. Nonetheless, nucleophilic attack at 3 provides isoosmabenzenes 4 a and 4 b, or opens the ring to produce 5 a and 5 b. We propose mechanisms to disclose the intrinsic connection between the six-membered metallacycles, and carry out DFT calculations to rationalize the regioselectivity of the nucleophilic addition reactions.
Reactions of the hydrido-butenylcarbyne complex [OsHCl2(≡CC(PPh3)=CHEt)(PPh3)2]BF4 (1) with nitriles RC≡N (R=2-cyclopropyl-2-oxopropyl, 3-amino-2-oxobutyl) lead to six-membered cyclic vinylidene complexes 3 and azavinylidene complexes 4, that is, iso-osmapyridiniums. Treatment of 1 with excess 2-formylbenzonitrile at reflux temperature in CHCl3 in the presence of air produces a fused osmapyridinium 8, which is first oxidized to the tricyclic iso-osmapyridinium derivative 7, then to iso-osmapyridinium 9, which contains a fused naphthalenone fragment. The conversion of iso-osmapyridinium 9 (with a vinylidene segment) to the iso-osmapyridinium compounds 10 and 11 (with azavinylidene segments) was achieved in the presence of a hydrogen halide, such as HCl or HI. The molecular structures of the complexes synthesized were confirmed by X-ray studies. Moreover, the aromatic stabilization energy and nucleus-independent chemical-shift values of the osmapyridiniums and the strain in the iso-osmapyridinium rings were investigated by DFT calculations.
A convenient and general strategy
has been developed to synthesize
stable iridapolycycles 5–8. Reaction
of arylacetylenes with iridium-hydride complex [IrH(CO)Cl(PPh3)3]BF4 via nucleophilic addition, oxidative
decarbonylation, and C–H bond activation results in the formation
of a series of iridacyclopentadiene derivatives, including benzo-iridacyclopentadiene 5, naphtho-iridacyclopentadiene 6, pyreno-iridacyclopentadiene 7, and thieno-iridacyclopentadiene 8. These iridapolycycles
display high thermal and air stability yet can be further functionalized
via facile ligand substitution reactions. As an example, complex 5 was used as a metallosynthon to react with 2,2′-dipyridyl
to give intensely luminescent Ir(III) complex 9 bearing
one C∧C and one N∧N ligands. Density
functional theory (DFT) calculations reveal that the lowest unoccupied
molecular orbitals (LUMOs) of iridapolycycles 5–8 are located on the phosphonium groups while the highest
occupied molecular orbitals (HOMOs) are mainly located on the metal-embedded
C∧C frameworks. Our method offers a sequential construction
strategy for constructing luminescent iridacycles, which potentially
allows facile tuning of the photoluminescence properties by modulating
the C∧C and N∧N moieties independently.
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