Advanced search

Structure and reactivity of new iridium complexes with bis(oxazoline)-phosphonito ligands

(2009) INORGANIC CHEMISTRY. 48(23). p.11415-11424
Author
Organization
Abstract
The synthesis and characterization of novel iridium(I) complexes bearing a neutral bis(oxazoline)phosphonite ligand, NOPON(Me2) (I), are reported. Numerous Ir(I) complexes have been isolated in high yields and characterized by spectroscopy and X-ray diffraction. [Ir(mu-Cl)(cod)](2) (cod = 1,5-cyclooctadiene) reacted with I to give the air-sensitive complex [IrCl(cod)(NOPON(Me2))] (1), which shows broad (1)H and (13)C{(1)H} NMR signals due to dynamic exchange equilibria involving the cod and the NOPON(Me2) ligands. Reaction between a solution of 1 and CO afforded the carbonyl complex [IrCl(CO)(NOPON(Me2))] (2), whose solid-state structure has been determined by X-ray diffraction. Cationic complexes have been obtained by using NaBAr(F) (BAr(F) = B[3,5-(CF(3))(2)C(6)H(3)](4)) as a chloride abstractor. The complex [Ir(cod)(NOPON(Me2))]BAr(F) (3) displays a mononuclear structure in the solid state with ligand I acting as a bidentate P,N chelating ligand. This complex is a precatalyst for the hydrogenation of alkenes. Oxidative addition of H(2) to 3 occurred either in solution or in the solid-state and this reaction allowed the isolation of the 32 electron, dinuclear dihydrido-bridged iridium(III) complex [IrH(mu-H)(NOPON(Me2))](2)(BAr(F))(2) (4), in which the NOPON(Me2) ligands exhibit a facial coordination mode. It contains only hydrides as bridging ligands and the Ir(2)(mu-H)(2) unit can be viewed as containing a formal Ir-Ir double bond or two 3c-2e bonds. Complex 3 has also been reacted with CO in solution and in the solid state, and this yielded the dicarbonyl derivative [Ir(CO)(2)(NOPON(Me2))]BAr(F) (5). A transmetalation reaction between 3 and [PdCl(2)(NCPh)(2)] afforded the cationic Pd(II) complex [PdCl(NOPON(Me2))]BAr(F) (6), which has been structurally characterized.
Keywords
HIGHLY ENANTIOSELECTIVE HYDROGENATION, BRIDGED DIIRIDIUM COMPLEX, C-H ACTIVATION, X-RAY CRYSTAL, COORDINATION CHEMISTRY, CATALYTIC OLIGOMERIZATION, DINUCLEAR COMPLEXES, IRON COMPLEXES, ETHYLENE, HYDRIDO

Citation

Please use this url to cite or link to this publication:

Chicago
Peloso, Riccardo, Roberto Pattacini, Catherine Cazin, and Pierre Braunstein. 2009. “Structure and Reactivity of New Iridium Complexes with Bis(oxazoline)-phosphonito Ligands.” Inorganic Chemistry 48 (23): 11415–11424.
APA
Peloso, R., Pattacini, R., Cazin, C., & Braunstein, P. (2009). Structure and reactivity of new iridium complexes with bis(oxazoline)-phosphonito ligands. INORGANIC CHEMISTRY, 48(23), 11415–11424.
Vancouver
1.
Peloso R, Pattacini R, Cazin C, Braunstein P. Structure and reactivity of new iridium complexes with bis(oxazoline)-phosphonito ligands. INORGANIC CHEMISTRY. 2009;48(23):11415–24.
MLA
Peloso, Riccardo, Roberto Pattacini, Catherine Cazin, et al. “Structure and Reactivity of New Iridium Complexes with Bis(oxazoline)-phosphonito Ligands.” INORGANIC CHEMISTRY 48.23 (2009): 11415–11424. Print.
@article{8536625,
  abstract     = {The synthesis and characterization of novel iridium(I) complexes bearing a neutral bis(oxazoline)phosphonite ligand, NOPON(Me2) (I), are reported. Numerous Ir(I) complexes have been isolated in high yields and characterized by spectroscopy and X-ray diffraction. [Ir(mu-Cl)(cod)](2) (cod = 1,5-cyclooctadiene) reacted with I to give the air-sensitive complex [IrCl(cod)(NOPON(Me2))] (1), which shows broad (1)H and (13)C\{(1)H\} NMR signals due to dynamic exchange equilibria involving the cod and the NOPON(Me2) ligands. Reaction between a solution of 1 and CO afforded the carbonyl complex [IrCl(CO)(NOPON(Me2))] (2), whose solid-state structure has been determined by X-ray diffraction. Cationic complexes have been obtained by using NaBAr(F) (BAr(F) = B[3,5-(CF(3))(2)C(6)H(3)](4)) as a chloride abstractor. The complex [Ir(cod)(NOPON(Me2))]BAr(F) (3) displays a mononuclear structure in the solid state with ligand I acting as a bidentate P,N chelating ligand. This complex is a precatalyst for the hydrogenation of alkenes. Oxidative addition of H(2) to 3 occurred either in solution or in the solid-state and this reaction allowed the isolation of the 32 electron, dinuclear dihydrido-bridged iridium(III) complex [IrH(mu-H)(NOPON(Me2))](2)(BAr(F))(2) (4), in which the NOPON(Me2) ligands exhibit a facial coordination mode. It contains only hydrides as bridging ligands and the Ir(2)(mu-H)(2) unit can be viewed as containing a formal Ir-Ir double bond or two 3c-2e bonds. Complex 3 has also been reacted with CO in solution and in the solid state, and this yielded the dicarbonyl derivative [Ir(CO)(2)(NOPON(Me2))]BAr(F) (5). A transmetalation reaction between 3 and [PdCl(2)(NCPh)(2)] afforded the cationic Pd(II) complex [PdCl(NOPON(Me2))]BAr(F) (6), which has been structurally characterized.},
  author       = {Peloso, Riccardo and Pattacini, Roberto and Cazin, Catherine and Braunstein, Pierre},
  issn         = {0020-1669},
  journal      = {INORGANIC CHEMISTRY},
  keyword      = {HIGHLY ENANTIOSELECTIVE HYDROGENATION,BRIDGED DIIRIDIUM COMPLEX,C-H ACTIVATION,X-RAY CRYSTAL,COORDINATION CHEMISTRY,CATALYTIC OLIGOMERIZATION,DINUCLEAR COMPLEXES,IRON COMPLEXES,ETHYLENE,HYDRIDO},
  language     = {eng},
  number       = {23},
  pages        = {11415--11424},
  title        = {Structure and reactivity of new iridium complexes with bis(oxazoline)-phosphonito ligands},
  url          = {http://dx.doi.org/10.1021/ic901579u},
  volume       = {48},
  year         = {2009},
}

Altmetric
View in Altmetric
Web of Science
Times cited: