Heinemann FW (2007)
Publication Status: Published
Publication Type: Journal article
Publication year: 2007
Publisher: WILEY-V C H VERLAG GMBH
Pages Range: 4364-4374
Journal Issue: 27
The P-2/N-2-coordinated cis-dihydridoiridium(III) chelate complexes (OC-6-13)-[IrH2(H(2)NnNH(2))(PR3)(2)]BF4 [PR3 = PPh3, H(2)NnNH(2) = 1,2-(H2N)(2)C6H4 (1a); (lR,2R)-(H2N)(2)C6Ho J(R,R)-dach) (1b); (R)-2,2'-diamino-1,1'-binaphthyI I(R)dabinj (1c); PR3 = PiPr(3), H(2)NnNH(2) = (R,R)-dach (2a), (R)dabin (2b); PR3 = PC gamma 3, H2NnNH(2) = (R)-dabin (3)] were obtained by treating the respective diamine ligands with labile precursors such as [1rH(2)(OCMe2)(2)(PPh3)2]BF4, [(ill-1,5C8Hl2)lr(PPh3)2]BF4, or [IrH5(PR3)(2)]/HBF4 (R = iPr, Cy). While oxidative addition of HCl to f(Tl'-1,5-C8H12)lrj(S,S)bdpcp)]BF4 [(S,S)-bdpcp = (lS,2S)-(Ph2P)2C5H8] yields the usual mononuclear adduct [(q4_l,5-C8H12)Ir(H)(Cl)((S,S)bdpcp)]BF4 (4), similar treatment of [(fl4_ 1,5-C8H12)Irj(R)binap)]BF4 furnishes the triply chlorido-bridged diiridium complex [j(R)-binap)2lr2H2(V-Cl)3jBF4 (5). Opening of the pCl bridges of 5 by N,N nucleophiles was used to synthesise the three diamine/(R)-binap complexes [lr(H)(Cl)(H2NnNH2fflR)-binap)jBF4 IH,NnNH2 (lR,2R)H2NCH(Ph)CH(Ph)NH2 j(R,R)-dpen) (6a), (R,R)-dach (6b), and H2NCMe2CMe2NH2 Itmen) (6c). Whereas the dihydrides [IrH2YR,R)-dachj(PR3)2]BF4 and [lrH2YR)-dabinj(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 [ee a. = 82-84 % (S)] in the presence of base. The crystal structures of la, 4, and 5 have been determined.
APA:
Heinemann, F.W. (2007). Synthesis and catalytic applications of chiral hydridoiridium(III) complexes with diamine/bis(monophosphane) and diamine/diphosphane coordination. European Journal of Inorganic Chemistry, 27, 4364-4374. https://doi.org/10.1002/ejic.200700380
MLA:
Heinemann, Frank Wilhelm. "Synthesis and catalytic applications of chiral hydridoiridium(III) complexes with diamine/bis(monophosphane) and diamine/diphosphane coordination." European Journal of Inorganic Chemistry 27 (2007): 4364-4374.
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