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An Extremely Bulky Tris(pyrazolyl)methanide: A Tridentate Ligand for the Synthesis of Heteroleptic Magnesium(II) and Ytterbium(II) Alkyl, Hydride, and Iodide Complexes
Author(s) -
Lalrempuia Ralte,
Stasch Andreas,
Jones Cameron
Publication year - 2015
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201403089
Subject(s) - deprotonation , chemistry , medicinal chemistry , hydride , ligand (biochemistry) , alkyl , tris , iodide , magnesium , methyl iodide , stereochemistry , inorganic chemistry , ion , organic chemistry , metal , biochemistry , receptor
The tris(pyrazolyl)methane compound HC(3‐Ad‐5‐Mepz) 3 [ 1 , 3‐Ad‐5‐Mepz=3‐(1‐adamantyl)‐5‐methylpyrazolyl] and its regioisomer, HC(3‐Ad‐5‐Mepz) 2 (3‐Me‐5‐Adpz), were synthesized and crystallographically characterized. Deprotonation of 1 with MeLi afforded the lithium complex [{κ 3 ‐N‐C(3‐Ad‐5‐Mepz) 3 }Li(thf)], which incorporates a tris(pyrazolyl)methanide ligand of unprecedented bulk. Reaction of 1 with MeMgI gave the ionic coordination complex [{κ 3 ‐N‐HC(3‐Ad‐5‐Mepz) 3 }MgMe]I, which was readily deprotonated to afford the neutral compound [{κ 3 ‐N‐C(3‐Ad‐5‐Mepz) 3 }MgMe]. The related magnesium butyl compound [{κ 3 ‐N‐C(3‐Ad‐5‐Mepz) 3 }MgBu] was prepared from the reaction of 1 and MgBu 2 . Treating this with LiAlH 4 or LiAlD 4 led to rare examples of terminal magnesium hydride/deuteride complexes, [{κ 3 ‐N‐C(3‐Ad‐5‐Mepz) 3 }MgH/D]. All neutral magnesium alkyl and hydride compounds were crystallographically authenticated. Reaction of [{κ 3 κN‐C(3‐Ad‐5‐Mepz) 3 }Li(thf)] with [YbI 2 (thf) 2 ] yielded the first structurally characterized f‐block tris(pyrazolyl)methanide complex, [{κ 3 ‐N‐C(3‐Ad‐5‐Mepz) 3 }YbI(thf)].