Reductive Trapping of [(OC)5W–W(CO)5]2− in a Mixed‐Valent SmII/III Calix[4]pyrrolide Sandwich. Issue 29 (14th June 2017)

• Record Type: Journal Article
• Authors: Deacon, Glen B.; Guo, Zhifang; Junk, Peter C.; Wang, Jun
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 29(2017)
• Page Start: 8486
• Page End: 8489
• Publication Date: 2017-06-14
• Subjects: calix[4]pyrrole -- lanthanoid complexes -- mixed valence -- organolanthanoids -- tungsten carbonyl; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201702636
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Reduction of tungsten hexacarbonyl by the divalent samarium(II) complex [Sm2 (N4 Et8 )(thf)4 ] ((N4 Et8 ) 4− = meso ‐octaethylcalix[4]pyrrolide) in toluene at ambient temperature gave the remarkable heteronuclear mixed‐valent samarium(II/III)/tungsten complex [{(thf)2 Sm II (N4 Et8 )Sm III (thf)}2 {(μ‐OC)2 W2 (CO)8 }], which features the trapping of a rare [W2 (CO)10 ] 2− anion with an unsupported W−W bond. Abstract : Rare mixed‐valent Sm II/III and Eu II/III calix[4]pyrrolide complexes were synthesized in good and repeatable yield by oxidation of relevant divalent metal precursors. One synthesis involves trapping an extremely rare anionic ditungsten decacarbonyl [W2 (CO)10 ] 2− unit with an unsupported W−W bond, achieved through a reductive coupling induced by the divalent samarium calix[4]pyrrolide complex.