These tools will no longer be maintained as of December 31, 2024. Archived website can be found here. PubMed4Hh GitHub repository can be found here. Contact NLM Customer Service if you have questions.


Pubmed for Handhelds

PUBMED FOR HANDHELDS

Search MEDLINE/PubMed

  • Title: Preparation and physical properties of early-late heterobimetallic compounds featuring Ir-M bonds (M = Ti, Zr, Hf).
    Author: Curley JJ, Bergman RG, Tilley TD.
    Journal: Dalton Trans; 2012 Jan 07; 41(1):192-200. PubMed ID: 22020701.
    Abstract:
    Treatment of Cp*Ir N(t)Bu (1) with the appropriate metallocene equivalent is an effective route for the preparation of the heterobimetallic complexes Cp*Ir(μ-N(t)Bu)MCp(2) (2-M, M = Ti, Zr, Hf). The electronic structures of the isostructural series of compounds, 2-M, are described with reference to single-crystal X-ray, Raman, UV-vis, and cyclic voltammetry data. Density functional theory (DFT) calculations were used to aid in the interpretation of this experimental work. Treatment of the zirconium or hafnium congeners with 2,6-lutidinium triflate leads to protonation of the Ir-M bond, to afford Cp*Ir(μ-N(t)Bu)(μ-H)MCp(2)OTf (3-M, M = Zr, Hf). Compound 3-Zr was characterized by single-crystal X-ray diffraction and independently prepared by the reaction of 1 and Cp(2)Zr(H)Cl in the presence of Me(3)SiOTf. In reactions analogous to those for 2-Zr, 2-Hf reacts with S(8) and aryl azides to insert an S-atom or aryl azide fragment into the metal-metal bond, yielding Cp*Ir(μ-N(t)Bu)(μ-S)HfCp(2) (6-Hf) and Cp*Ir(μ-N(t)Bu)(N(3)Ph)HfCp(2) (4-Hf), respectively. Heating 4-Hf results in N(2) extrusion to form Cp*Ir(μ-N(t)Bu)(NPh)HfCp(2) (5-Hf). The kinetics of the latter reaction were studied to obtain activation parameters and a Hammett trend; these data are compared to those for the analogous reaction involving Ir-Zr heterobimetallics.
    [Abstract] [Full Text] [Related] [New Search]