Solid-State and Dynamic Solution Behavior of a Cationic, Two-Coordinate Gold(I) π-Allene Complex

@article{Brown2010SolidStateAD,
  title={Solid-State and Dynamic Solution Behavior of a Cationic, Two-Coordinate Gold(I) $\pi$-Allene Complex},
  author={Timothy J. Brown and Atsushi Sugie and Marina G. Dickens and Ross A. Widenhoefer},
  journal={Organometallics},
  year={2010},
  volume={29},
  pages={4207-4209}
}
The cationic gold π-allene complex {[P(t-Bu)2o-biphenyl]Au[η2-H2C═C═C(CH3)2]}+SbF6− was isolated in 98% yield from reaction of 3-methyl-1,2-butadiene with a mixture of [P(t-Bu)2o-biphenyl]AuCl and AgSbF6 and was characterized by X-ray crystallography and variable-temperature NMR spectroscopy. These studies revealed preferential binding of gold to the less substituted C═C bond of the allene in both the solid state and solution and also revealed fluxional behavior consistent with π-face exchange… 
61 Citations

Figures from this paper

Structures and dynamic solution behavior of cationic, two-coordinate gold(I)-π-allene complexes.
A family of seven cationic gold complexes that contain both an alkyl substituted π-allene ligand and an electron-rich, sterically hindered supporting ligand was isolated in >90% yield and
Synthesis and Structure of Cationic Phosphine Gold(I) Enol Ether Complexes
Cationic {[(t-Bu)2(o-biphenyl)P]Au(enol ether)}+SbF6– and {[(t-Bu)3P]Au(enol ether)}+SbF6– complexes were isolated and characterized by NMR spectroscopy and X-ray crystallography. For three of the
Syntheses, X-ray Crystal Structures, and Solution Behavior of Cationic, Two-Coordinate Gold(I) η2-Diene Complexes
A family of cationic gold π-diene complexes of the form {[P(t-Bu)2o-biphenyl]Au(η2-diene)}+SbF6– were isolated in >80% yield from reaction of various dienes with a mixture of [P(t-Bu)2o-biphenyl]AuCl
Synthesis and Structure of Dicationic, Bis(gold) π-Alkene Complexes Containing a 2,2′-Bis(phosphino)biphenyl Ligand
The dicationic bis(gold)-biarylphosphine π-alkene complexes {(P–P)[Au(π-alkene)]2}2+2SbF6– [P–P = 2,2′-bis(di-tert-butylphosphino)biphenyl; alkene = isobutylene, 1-pentene] were isolated in >95%
Synthesis and study of cationic, two-coordinate triphenylphosphine-gold-π complexes.
TLDR
These complexes were characterized by low-temperature, multinuclear NMR spectroscopy without isolation and underwent facile intermolecular exchange with free ligand and competitive displacement by weak σ donors, such as trifluoromethane sulfonate.
Dinuclear NHC Gold(I) Allenyl and Propargyl Complexes: An Experimental and Theoretical Study
The synthesis and isolation of the dinuclear NHC gold(I) allene-1,3-diyl complex Ph(IPrAu)C═C═CH(AuIPr) and the dinuclear NHC gold(I) propyne-1,3-diyl complex Ph(IPrAu)CH–C≡C–Au(IPr) are presented.
Twists and turns of platinum-allene complexes: NMR techniques for the study of the dynamic behavior in solution
Classic (dynamic exchange line-shape analysis) and novel (SSTD NMR) NMR techniques have been applied in order to obtain the kinetic and thermodynamic parameters of the three main processes occurring
Formation of Iridium(III) Allene Complexes via Isomerization of Internal Alkynes
Syntheses of the alkyne complexes (POCOP)Ir(η2-RC≡CR) (1-DPA, R = Ph; 1-Oct, R = C3H7; 1-Hex, R = C2H5; POCOP = 2,6-bis(di-tert-butylphosphonito)benzene) are reported. 1-DPA is stable in both the
Mechanism of the gold(III)-catalyzed isomerization of substituted allenes to conjugated dienes: a DFT study.
TLDR
Calculated results reveal that the unbound nitroso compound acts as a better proton transferring agent in the isomerization process and utilizes its own nitrogen atom to carry the proton.
...
...

References

SHOWING 1-10 OF 12 REFERENCES
J. Am. Chem. Soc
  • J. Am. Chem. Soc
  • 1985
J. Am. Chem. Soc. J. Am. Chem. Soc. Organometallics
  • J. Am. Chem. Soc. J. Am. Chem. Soc. Organometallics
  • 1967
J. Am. Chem. Soc. Organometallics Organometallics Organometallics J. Organomet. Chem. Organometallics Organometallics Organometallics
  • J. Am. Chem. Soc. Organometallics Organometallics Organometallics J. Organomet. Chem. Organometallics Organometallics Organometallics
  • 1516
J. Am. Chem. Soc. Benet-Buchholz, J.; Echavarren, A. M. Angew. Chem., Int. Ed
  • J. Am. Chem. Soc. Benet-Buchholz, J.; Echavarren, A. M. Angew. Chem., Int. Ed
  • 2006
Inorg. Chim. Acta Rev. Chem. Rev. J. Organomet. Chem. J. Organomet. Chem. Organomet. Chem. Brion, F. Angew. Chem., Int. Ed. Engl
  • Inorg. Chim. Acta Rev. Chem. Rev. J. Organomet. Chem. J. Organomet. Chem. Organomet. Chem. Brion, F. Angew. Chem., Int. Ed. Engl
  • 1973
J. Organomet. Chem. J. Organomet. Chem
  • J. Organomet. Chem. J. Organomet. Chem
  • 1969
J. Am. Chem. Soc
  • J. Am. Chem. Soc
  • 1243
Proc. Natl. Acad. Sci
  • Proc. Natl. Acad. Sci
  • 2009
Chem. Soc. Chem. Commun
  • Chem. Soc. Chem. Commun
  • 2009
Inorg. Chem
  • Inorg. Chem
  • 1979
...
...