An extremely bulky tris(pyrazolyl)methanide: a tridentate ligand for the synthesis of heteroleptic magnesium(II) and ytterbium(II) alkyl, hydride, and iodide complexes.
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 MgBu2 . Treating this with LiAlH4 or LiAlD4 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 [YbI2 (thf)2 ] yielded the first structurally characterized f-block tris(pyrazolyl)methanide complex, [{κ(3) -N-C(3-Ad-5-Mepz)3 }YbI(thf)].
School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia), Fax: (+61) 3-9905-4597.
Ralte
R
Lalrempuia
Andreas
A
Stasch
Cameron
C
Jones
calcium; magnesium; reduction; steric bulk; ytterbium