SYNTHESIS, STRUCTURE, SPECTROSCOPY, AND REACTIVITY OF A METALLATHIABENZENE1

@article{Bleeke1999SYNTHESISSS,
  title={SYNTHESIS, STRUCTURE, SPECTROSCOPY, AND REACTIVITY OF A METALLATHIABENZENE1},
  author={John R. Bleeke and Robert Behm and Yun Feng Xie and Michael Yen-Nan Chiang and Andrea K Robinson and Alicia M. Beatty},
  journal={Journal of the American Chemical Society},
  year={1999},
  volume={121},
  pages={595-596}
}
A rare example of a stable metallabenzene complex has been synthesized in three high-yield steps from (Cl)Ir(PEt3)3. In the first step, (Cl)Ir(PEt3)3 is treated with potassium 2,4-dimethylpentadienide to produce the metallacyclohexadiene complex mer-CHC(Me)CHC(Me)CH2Ir(PEt3)3(H) (1b) via metal-centered CH bond activation. Treatment of 1b with methyl trifluoromethanesulfonate removes the hydride ligand, producing [CHC(Me)CHC(Me)CH2Ir(PEt3)3]+O3SCF3- (2). Finally, deprotonation of 2 with base… Expand
76 Citations
Diphenylamine-Substituted Osmanaphthalyne Complexes: Structural, Bonding, and Redox Properties of Unusual Donor-Bridge-Acceptor Systems.
TLDR
Diarylamine-substituted osmanaphthalyne complexes that feature two redox centers linked by the rigid skeleton of the metallacycle are successfully synthesized and characterized by 1 H, 13 C, and 31 P NMR spectroscopy, ESI-MS, and elemental analysis. Expand
Synthesis, Structure, and Reactivity of an Osmacyclopentene Complex
Treatment of OsCl2(PPh3)2(CH═C(PPh3)CH(OH)-η2-C≡CH) (1) with PPh3 and Bu4NCl in CH2Cl2 under air gave paramagnetic osmacyclopentene [OsCl2(PPh3)2(CH═C(PPh3)CH(OH)C(═CH(PPh3)))]Cl (5). Heating theExpand
Chemistry of Iridium(I) Cyclooctadiene Compounds with Thiapentadienyl, Sulfinylpentadienyl, and Butadienesulfonyl Ligands
The metathesis reaction of [(η4-COD)Ir(μ-Cl)]2 (4) with two equivalents of the sodium thiapentadienide (1Na) or potassium sulfinylpentadienide salt (2K) led to the formation of the correspondingExpand
Synthesis of rhenabenzenes from the reactions of rhenacyclobutadienes with ethoxyethyne.
TLDR
The NMR spectroscopic and X-ray structural data, as well as the aromatic stabilization energy (ASE) values, suggest that the rhenabenzenes are aromatic, with extensive delocalized π character. Expand
Synthesis and characterization of rhenabenzyne complexes.
TLDR
The NMR spectroscopic and structural data as well as the aromatic stabilization energy (ASE) and nucleus-independent chemical-shift (NICS) values suggest that these rhenabenzynes have aromatic character. Expand
Synthesis and characterization of a rhenabenzyne complex.
TLDR
The preparation and structural characterization of the first stable rhenabenzyne complex is reported, which can be stored under nitrogen at room temperature for a week without appreciable decomposition and can be readily identified by NMR spectroscopy. Expand
Remarkable transformations of thiophene ligands in their pentamethylcyclopentadienyl iridium (Cp*Ir) complexes
Abstract The cationic η5-2,5-dimethylthiophene complex Cp*Ir(η5-2,5-Me2T)2+ (1) is the entry point for the synthesis of a variety of complexes resulting from nucleophilic attack on or reduction of 1.Expand
Interconversion of metallabenzenes and cyclic η2-allene-coordinated complexes.
TLDR
Investigation shows that the ratio of 7 and 8 is highly dependent on the amount of the acid in the reaction, which could react with water to give carbonyl complex. Expand
π Delocalization in iridathiabenzenes
Abstract Fenske–Hall calculations were carried out for (PEt3)3Ir(C7H9) (1), [(PEt3)3Ir(C6H8S)]+ (2), [(S-t-but)(PEt3)2]Ir(C6H8S) (3), and [(S-t-but)(PMet3)3]Ir(C6H8S) (4) in order to compare theExpand
A triple-decker complex with a central metallabenzene.
TLDR
The synthesis and characterization of the first tripledecker complex with a central metallabenzene and the structure of 2 was deduced on the basis of its mass spectrum and 1H as well as 13C{1H} NMR spectroscopic data. Expand
...
1
2
3
4
5
...