Labilizing the Photoinert: Extraordinarily Facile Photochemical Ligand Ejection in an [Os(N^N)3]2+ Complex. Issue 36 (3rd August 2016)

• Record Type: Journal Article
• Authors: Scattergood, Paul A.; Ross, Daniel A. W.; Rice, Craig R.; Elliott, Paul I. P.
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 36(2016)
• Page Start: 10697
• Page End: 10701
• Publication Date: 2016-08-03
• Subjects: complexes -- isomers -- osmium -- photochemistry -- triazole; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201604959
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Whilst [Os(N^N)3 ] 2+ complexes are supposed to be photochemically inert to ligand loss, the complex [Os(btz)3 ] 2+ (btz=1, 1′‐dibenzyl‐4, 4′‐bi‐1, 2, 3‐triazolyl) undergoes unprecedented photolytic reactivity to liberate free btz ( Φ 363 ≈1.2 %). Further, both cis and trans isomers of the photodechelated ligand‐loss solvento intermediate [Os(κ 2 ‐btz)2 (κ 1 ‐btz)(NCMe)] 2+ are unambiguously observed and characterized by NMR spectroscopy and mass spectrometry. Abstract : Defying convention : The extraordinary ligand ejection photochemistry of the complex [Os(btz)3 ] 2+ in donor solvents is reported along with observation and characterization of both cis and trans isomers of the ligand‐loss intermediate [Os(κ 2 ‐btz)2 (κ 1 ‐btz)(NCMe)] 2+ (btz=1, 1′‐dibenzyl‐4, 4′‐bi‐1, 2, 3‐triazolyl).