A Triarylated 1, 2, 3‐Triazol‐5‐ylidene Ligand with a Redox‐Active Ferrocenyl Substituent for Rhodium(I)‐Catalyzed Hydroformylation of 1‐Octene. Issue 9 (3rd March 2017)

• Record Type: Journal Article
• Authors: Aucamp, Danielle; Witteler, Tim; Dielmann, Fabian; Siangwata, Shepherd; Liles, David C.; Smith, Gregory S.; Bezuidenhout, Daniela I.
• Is Part Of: European journal of inorganic chemistry. Issue 9(2017)
• Page Start: 1227
• Page End: 1236
• Publication Date: 2017-03-03
• Subjects: Rhodium -- Hydroformylation -- Mesoionic carbene -- Redox‐active ferrocene -- Heterometallic complexes; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700164
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : A series of rhodium(I)–1, 2, 3‐triazol‐5‐ylidene (trz) complexes are described, containing either a novel triarylated trz ligandA′ (N1, N3‐arylated, C4‐ferrocenyl) {complexes1, [Rh(A′ )Cl(cod)];4, [Rh(A′ )Cl(CO)2 ]}, or N3‐alkylated triazolylidenes with a C4‐ferrocenyl {2, [Rh(B′ )Cl(cod)];5, [Rh(B′ )Cl(CO)2 ]} or C4‐phenyl substituent {3, [Rh(C′ )Cl(cod)];6, [Rh(C′ )Cl(CO)2 ]}. The free mesoionic carbene (MIC)A′ is structurally characterized and its electronic properties evaluated by employing the complex [Pd(Br)2 ( i Pr2 ‐bimy)(A′ )] (7 ) in an NMR spectroscopic analysis method. The redox activity ofA′ is exploited, and the chemically oxidized precursorAox and complex4ox are isolated. The mesoionic carbene complexes1 –3, as well as in situ oxidized1 ox, are used as homogeneous catalysts for the hydroformylation of 1‐octene for the first time, and the influence of chemical oxidation of the catalyst on the activity and chemo‐ and regioselectivity of the catalyst precursor1 is evaluated. Abstract : A ligand‐design strategy, utilizing the redox‐tuning of a new triarylated 1, 2, 3‐triazol‐5‐ylidene ligand, incorporating a ferrocenyl substituent, was followed in the preparation of Rh I –triazolylidene catalysts for the hydroformylation of aliphatic olefins.