Chiral (SO)-N-(SO) Sulfoxide Pincer Complexes of Mg, Rh, and Ir: N-H Activation and Selective Sulfoxide Reduction upon Ligand Coordination

Locke H, Herrera AC, Heinemann FW, Linden A, Frieß S, Schmid B, Dorta R (2015)

Publication Status: Published

Publication Type: Journal article

Publication year: 2015

Journal

Organometallics American Chemical Society

Publisher: American Chemical Society

Book Volume: 34

Pages Range: 1925-1931

DOI: 10.1021/acs.organomet.5b00178

Abstract

Multigram quantities of the optically pure amino bis-sulfoxide ligand (S,S)-bis(4-tert-butyl-2-(p-tolylsulfinyl)phenyl)amine ((S,S)-3) are accessible by in situ lithiation of bis(2-bromo-4-tert-butylphenyl)amine (1) followed by a nudeophilic displacement reaction with Andersen's sulfinate 2. Deprotonation of (S,S)-3 with MgPh2 yields the magnesium amido bis-sulfoxide salt (S,S)-4 quantitatively. Metathetical exchange of (S,S)-4 with [RhCl(COE)(2)](2) affords the optically pure pseudo-C-2-symmetric Rh(I) amido bis-sulfoxide pincer complex mer-(R,R)-[Rh(bis(4-(tert-butyl)-2-(p-tolylsulfinyl)phenyl)amide)(COE)] (mer-(R,R)-5). This complex reacts with 3 equiv of HCl to give the facial Rh(III) complex fac-(S,R,R)-[Rh(bis(4-(tert-butyl)-2-(p-tolylsulfinyl)phenyl)amine)-Cl-3] (fac-(S,R,R)-6), in which one of the sulfoxide functions has been reduced to the sulfide and in which the resulting sulfoxide-sulfide-amine ligand is facially coordinated. The same complexes S and 6 form in a 1:2 ratio in a disproportionation reaction when [RhCl(COE)(2)](2) is treated with 2 equiv of neutral ligand 3. N-H activation is directly observed in the reaction of [IrCl(COE)(2)](2) with 3, affording the amido-hydrido-Ir(III) complex [Ir(bis(4-(tert-butyl)-2-(p-tolylsulfinyl)phenyl)amide)(Cl)(H)(COE)] (8).

Authors with CRIS profile

Harald Locke Sonderforschungsbereich 953/3 Synthetische Kohlenstoffallotrope Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie Sibylle Frieß Lehrstuhl für Anorganische und Allgemeine Chemie Bernhard Schmid Lehrstuhl für Theoretische Chemie Romano Dorta Professur für Anorganische Chemie

How to cite

APA:

Locke, H., Herrera, A.C., Heinemann, F.W., Linden, A., Frieß, S., Schmid, B., & Dorta, R. (2015). Chiral (SO)-N-(SO) Sulfoxide Pincer Complexes of Mg, Rh, and Ir: N-H Activation and Selective Sulfoxide Reduction upon Ligand Coordination. Organometallics, 34, 1925-1931. https://doi.org/10.1021/acs.organomet.5b00178

MLA:

Locke, Harald, et al. "Chiral (SO)-N-(SO) Sulfoxide Pincer Complexes of Mg, Rh, and Ir: N-H Activation and Selective Sulfoxide Reduction upon Ligand Coordination." Organometallics 34 (2015): 1925-1931.

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