C-2-Symmetric (SO)N(SO) Suloxide Pincer Complexes of Mg and Pd: Helicity Switch by Ambidentate S/O-Coordination and Isolation of a Chiral Pd-Sulfenate

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Details zur Publikation

Autorinnen und Autoren: Seidel F, Frieß S, Heinemann F, Chelouan A, Scheurer A, Grasruck A, Herrera AC, Dorta R
Zeitschrift: Organometallics
Jahr der Veröffentlichung: 2018
Band: 37
Seitenbereich: 1160-1171
ISSN: 0276-7333


Abstract

Quinine-based (R)-tert-butylsulfinate 3 reacts with tris-lithiated bis-arylamide 2 to afford gram-quantities of optically pure (S*O)N(S*O) sulfoxide pincer ligand (R,R)-4. Deprotonation of (R,R)-4 and p-Tol-substituted analogue (S,S)-5 with MgPh2 and BnK yields respective Mg and K amido-bis-sulfoxides 69. In Mg complexes 6 and 7, the sulfoxide functions are O-coordinated, thereby imparting a pronounced helicity to the ligand backbone. Transmetalation of 6 and 7 with [PdCl2(NCPh)2] affords the S,S-coordinated C2-symmetric and the O,S-coordinated C1-symmetric chlorido complexes 10 and 11, respectively, and reaction of potassium amides 8 and 9 with [PdCl(CH3)(COD)] leads to methyl-palladium pincer complexes 12 and 13, respectively. The crystal structures of 6, 7, 12, and 13 reveal a chameleonic ligand system with predictable behavior: (R)-configured 4 induces pronounced λ backbone helicity in the O-coordinated Mg-complex and weaker δ helicity in S-coordinated Pd-complexes, while (S)-configured ligand 5 mirrors this stereochemistry. S-Coordination induces stronger, C2-symmetric, steric crowding in the head-on quadrants compared to O-coordination. When (R,R)-4 is reacted with 2 equiv of [Pd(CH3)2(tmeda)], crystalline chiral Pd-sulfenate complex 16 forms by elimination of iso-butene and methane with inversion of configuration at the sulfenate S atom.


FAU-Autorinnen und Autoren / FAU-Herausgeberinnen und Herausgeber

Chelouan, Ahmed Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Dorta, Romano Prof. Dr.
Professur für Anorganische Chemie
Frieß, Sibylle
Professur für Anorganische Chemie
Grasruck, Alexander
Professur für Anorganische Chemie
Heinemann, Frank Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Herrera, Alberto Cesar
Professur für Anorganische Chemie
Scheurer, Andreas Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Seidel, Falk
Lehrstuhl für Anorganische und Allgemeine Chemie


Zitierweisen

APA:
Seidel, F., Frieß, S., Heinemann, F., Chelouan, A., Scheurer, A., Grasruck, A.,... Dorta, R. (2018). C-2-Symmetric (SO)N(SO) Suloxide Pincer Complexes of Mg and Pd: Helicity Switch by Ambidentate S/O-Coordination and Isolation of a Chiral Pd-Sulfenate. Organometallics, 37, 1160-1171. https://dx.doi.org/10.1021/acs.organomet.8b00038

MLA:
Seidel, Falk, et al. "C-2-Symmetric (SO)N(SO) Suloxide Pincer Complexes of Mg and Pd: Helicity Switch by Ambidentate S/O-Coordination and Isolation of a Chiral Pd-Sulfenate." Organometallics 37 (2018): 1160-1171.

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Zuletzt aktualisiert 2019-06-01 um 01:10