Magnesium Reagents Featuring a 1, 1′‐Bis(o‐carborane) Ligand Platform. Issue 38 (26th July 2017)

• Record Type: Journal Article
• Authors: Axtell, Jonathan C.; Kirlikovali, Kent O.; Dziedzic, Rafal M.; Gembicky, Milan; Rheingold, Arnold L.; Spokoyny, Alexander M.
• Other Names: Bregadze Vladimir I. guestEditor.; Xie Zuowei guestEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 38/39(2017)
• Page Start: 4411
• Page End: 4416
• Publication Date: 2017-07-26
• Subjects: Carboranes -- Boron -- Cluster compounds -- Tin -- Electronic structure; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700604
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The synthesis of two bis(carboranyl) (bc ) magnesium reagents is described. Treatment of 1, 1′‐bis( o ‐carborane) (H2 ‐bc ) or 8, 8′, 9, 9′, 10, 10′, 12, 12′‐octamethyl‐1, 1′‐bis( o ‐carborane) (H2 ‐Mebc ) with Mg( n Bu)2 in 1, 2‐dimethoxyethane (DME) affords (bc )Mg(DME)2 (1a, b ) as crystalline solids. The magnesium compounds, which have been characterized by NMR spectroscopy and single‐crystal X‐ray crystallography in the case of1a, serve as competent Grignard‐type reagents to generatebc ‐containing species of tin from Me2 SnCl2 (2a, b ). The type of substitution of the bis( o ‐carboranyl) ligand framework is found to strongly affect the electronic character of the tin center, as judged by 119 Sn NMR spectroscopy. The disclosed compounds, which are stable solids under an atmosphere of dry nitrogen gas at room temperature, provide a new class ofbc ‐transfer reagents. Abstract : A well‐defined class of Mg‐based 1, 1′‐bis( o ‐carborane) reagents was prepared and used for group‐transfer chemistry toward Sn‐based electrophiles. The boron‐cluster‐based ligand, which behaves as a strongly electron‐withdrawing substituent, presents a frontier molecular orbital picture distinct from those of analogous biphenyl‐based compounds.