A Scandium‐Stabilized Diisophosphaethynolate Ligand: [OCPPCO]4−. Issue 4 (21st December 2017)

• Record Type: Journal Article
• Authors: Grant, Lauren N.; Pinter, Balazs; Manor, Brian C.; Grützmacher, Hansjörg; Mindiola, Daniel J.
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 4(2018)
• Page Start: 1049
• Page End: 1052
• Publication Date: 2017-12-21
• Subjects: OCP reduction -- OCPPCO -- phosphorus -- radical coupling -- scandium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201710757
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The first example of the OCPPCO ligand, diisophosphaethynolate, is reported via reductive coupling of a Sc−OCP precursor. Upon reduction with KC8, isolation of the dinuclear complex, namely [K(OEt2 )]2 [(nacnac)Sc(OAr)]2 (OCPPCO), is observed, leading to a unique motif [OCPPCO] 4−, stabilized by two scandium centers. Detailed NMR spectra of all complexes as well as IR and single crystal X‐ray studies were obtained to fully elucidate the nature of these complexes in solution as well as in the solid state. Theory is combined to probe the electronic structure and orbitals responsible for the bonding interactions in the Sc−OCPPCO−Sc skeleton but also to compare to the linear mode observed in the precursor. Abstract : The OCPPCO ligand, diisophosphaethynolate, formed by reductive coupling of a Sc−OCP precursor, is reported. Upon reduction with KC8, isolation of the dinuclear complex, [K(OEt2 )]2 [(nacnac)Sc(OAr)]2 (OCPPCO), is observed, leading to a unique motif [OCPPCO] 4− stabilized by two scandium centers. NMR, IR, and X‐ray diffraction were used to study these complexes in solution as well as in the solid state.