Chiral Ir(I) and Ir(III) complexes [Ir{(R)-binap} (1,2-diamine)]Cl and trans-[Ir(H)(2){(R)-binap} (1,2-diamine)]Cl: synthesis and catalytic applications

Dahlenburg L, Kramer D, Heinemann FW (2010)

Publication Status: Published

Publication Type: Journal article

Publication year: 2010

Journal

Journal of Coordination Chemistry Taylor & Francis: STM, Behavioural Science and Public Health Titles / Taylor & Francis

Publisher: TAYLOR & FRANCIS LTD

Book Volume: 63

Pages Range: 2673-2684

Journal Issue: 14-16

DOI: 10.1080/00958971003746108

Abstract

The P-2,N-2-coordinated iridium(I) chelate complexes [Ir{(R)-binap}(1,2-diamine)]Cl, where (R)-binap = (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl and 1,2-diamine = H2NCMe2 CMe2NH2 (tmen) (1), (1R,2R)-H2NCH(Ph)CH(Ph)NH2 [(R,R)-dpen] (2), or cyclo-(1R,2R)-1,2-(H2N)(2)C6H10 [(R,R)-dach] (3), were formed by treating [{(R)-binap}(2)Ir-2(mu-Cl)(2)] with the respective N,N ligand in inert solvents at ambient conditions. They reacted with methanol in benzene or toluene at reflux producing dihydridoiridium(III) complexes, trans-[Ir(H)(2){(R)-binap}(1,2-diamine)]Cl [1,2-diamine tmen (4), (R,R)-dpen (5), or (R,R)-dach (6)]. Compounds 4-6 are base-free (albeit rather slow) catalysts for both the transfer hydrogenation of acetophenone and the hydrogenation of the ketone with molecular hydrogen, giving (S)-1-phenylethanol with moderate enantioselectivities (ee(max) : 74%). A cyclometallated hydridoiridium(III) complex, characterized as (OC-6-54)-[Ir(H)(Cl){(R,R)-binap}{C6H4-2-[(R,R)-CH(NH2)CH(Ph)N=CMe2]-kappa C-1,kappa N-alpha}] (7) by single-crystal X-ray diffraction, was identified as one of the products formed from [{(R)-binap}(2)Ir-2(mu-Cl)(2)] and the (R,R)-dpen ligand in acetone under hydrogen.

Authors with CRIS profile

Lutz Dahlenburg Lehrstuhl für Anorganische und Metallorganische Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie

How to cite

APA:

Dahlenburg, L., Kramer, D., & Heinemann, F.W. (2010). Chiral Ir(I) and Ir(III) complexes [Ir{(R)-binap} (1,2-diamine)]Cl and trans-[Ir(H)(2){(R)-binap} (1,2-diamine)]Cl: synthesis and catalytic applications. Journal of Coordination Chemistry, 63(14-16), 2673-2684. https://doi.org/10.1080/00958971003746108

MLA:

Dahlenburg, Lutz, Dagmar Kramer, and Frank Wilhelm Heinemann. "Chiral Ir(I) and Ir(III) complexes [Ir{(R)-binap} (1,2-diamine)]Cl and trans-[Ir(H)(2){(R)-binap} (1,2-diamine)]Cl: synthesis and catalytic applications." Journal of Coordination Chemistry 63.14-16 (2010): 2673-2684.

BibTeX: Download