An Extremely Bulky Tris(pyrazolyl)methanide: A Tridentate Ligand for the Synthesis of Heteroleptic Magnesium(II) and Ytterbium(II) Alkyl,Hydride, and Iodide Complexes |
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| Authors: | Dr Ralte Lalrempuia Dr Andreas Stasch Prof Cameron Jones |
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| Institution: | School of Chemistry, Monash University, PO Box 23, Melbourne, VIC, 3800 (Australia), Fax: (+61)?3‐9905‐4597 |
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| Abstract: | 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 {κ3‐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 {κ3‐N‐HC(3‐Ad‐5‐Mepz)3}MgMe]I, which was readily deprotonated to afford the neutral compound {κ3‐N‐C(3‐Ad‐5‐Mepz)3}MgMe]. The related magnesium butyl compound {κ3‐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, {κ3‐N‐C(3‐Ad‐5‐Mepz)3}MgH/D]. All neutral magnesium alkyl and hydride compounds were crystallographically authenticated. Reaction of {κ3κN‐C(3‐Ad‐5‐Mepz)3}Li(thf)] with YbI2(thf)2] yielded the first structurally characterized f‐block tris(pyrazolyl)methanide complex, {κ3‐N‐C(3‐Ad‐5‐Mepz)3}YbI(thf)]. |
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| Keywords: | calcium magnesium reduction steric bulk ytterbium |
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