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Dahlenburg, Lutz; Menzel, Ralf; Heinemann, Frank W.

Synthesis and Catalytic Applications of Chiral Hydridoiridium(III) Complexes with Diamine/Bis(monophosphane) and Diamine/Diphosphane Coordination

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  • Media type: E-Article
  • Title: Synthesis and Catalytic Applications of Chiral Hydridoiridium(III) Complexes with Diamine/Bis(monophosphane) and Diamine/Diphosphane Coordination
  • Contributor: Dahlenburg, Lutz; Menzel, Ralf; Heinemann, Frank W.
  • Published: Wiley, 2007
  • Published in: European Journal of Inorganic Chemistry, 2007 (2007) 27, Seite 4364-4374
  • Language: English
  • DOI: 10.1002/ejic.200700380
  • ISSN: 1434-1948; 1099-0682
  • Keywords: Inorganic Chemistry
  • Origination:
  • Footnote:
  • Description: AbstractThe P2/N2‐coordinated cis‐dihydridoiridium(III) chelate complexes (OC‐6‐13)‐[IrH2(H2N∩NH2)(PR3)2]BF4 [PR3 = PPh3, H2N∩NH2 = 1,2‐(H2N)2C6H4 (1a); (1R,2R)‐(H2N)2C6H10 {(R,R)‐dach} (1b); (R)‐2,2′‐diamino‐1,1′‐binaphthyl {(R)‐dabin} (1c); PR3 = PiPr3, H2N∩NH2 = (R,R)‐dach (2a), (R)‐dabin (2b); PR3 = PCy3, H2N∩NH2 = (R)‐dabin (3)] were obtained by treating the respective diamine ligands with labile precursors such as [IrH2(OCMe2)2(PPh3)2]BF4, [(η4‐1,5‐C8H12)Ir(PPh3)2]BF4, or [IrH5(PR3)2]/HBF4 (R = iPr, Cy). While oxidative addition of HCl to [(η4‐1,5‐C8H12)Ir{(S,S)‐bdpcp}]BF4 [(S,S)‐bdpcp = (1S,2S)‐(Ph2P)2C5H8] yields the usual mononuclear adduct [(η4‐1,5‐C8H12)Ir(H)(Cl){(S,S)‐bdpcp}]BF4 (4), similar treatment of [(η4‐1,5‐C8H12)Ir{(R)‐binap}]BF4 furnishes the triply chlorido‐bridged diiridium complex [{(R)‐binap}2Ir2H2(μ‐Cl)3]BF4 (5). Opening of the μ‐Cl bridges of 5 by N,N nucleophiles was used to synthesise the three diamine/(R)‐binap complexes [Ir(H)(Cl)(H2N∩NH2){(R)‐binap}]BF4 [H2N∩NH2 = (1R,2R)‐H2NCH(Ph)CH(Ph)NH2 {(R,R)‐dpen} (6a), (R,R)‐dach (6b), and H2NCMe2CMe2NH2 {tmen} (6c). Whereas the dihydrides [IrH2{(R,R)‐dach}(PR3)2]BF4 and [IrH2{(R)‐dabin}(PR3)2]BF4 (R = iPr, Ph) are only poor (pre)catalysts for the enantioselective hydrogenation of acetophenone, complexes 6a–c catalyze the formation of 1‐phenylethanol in good enantiomeric excess [eemax = 82–84 % (S)] in the presence of base. The crystal structures of 1a, 4, and 5 have been determined. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)