Synthesis and characterisation of bulky guanidines and phosphaguanidines: precursors for low oxidation state metallacycles

Jin, Guoxia, Jones, Cameron, Junk, Peter C., Lippert, Kai-Alexander, Rose, Richard P., and Stasch, Andreas (2009) Synthesis and characterisation of bulky guanidines and phosphaguanidines: precursors for low oxidation state metallacycles. New Journal of Chemistry, 33 (1). pp. 64-75.

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Reactions of alkali metal amides or phosphides with the bulky carbodiimide, ArN[double bond, length as m-dash]C[double bond, length as m-dash]NAr (Ar = C6H3Pri2-2,6), followed by aqueous work-ups, have yielded several guanidines, ArNC(NR2)N(H)Ar (R = cyclohexyl (GisoH) or Pri (PrisoH); NR2 = cis-NC5H8Me2-2,6 (PipisoH)), a bifunctional guanidine, {ArNCN(H)Ar}2{µ-N(C2H4)2N} (Pip(GisoH)2), and two phosphaguanidines, ArNC(PR2)N(H)Ar (R = cyclohexyl (CyP-GisoH) or Ph (PhP-GisoH)). A very bulky guanidine, ArNC{N(Ar)SiMe3}N(H)Ar (ArSi-Giso), and an aryl coupled bifunctional guanidine, {ArN(H)C(NPri2)NC6H2Pri2-2,6-}2 (PrisoH)2, have been prepared by other routes. All compounds have been crystallographically characterised and shown to exist in a number of isomeric forms in the solid state. These appear to be largely retained in solution. The deprotonation of GisoH with BunLi in either hexane or THF led to crystallographically characterised dimeric and monomeric complexes respectively, viz. [Li{Li(κ2-N,N'-Giso)2}] and [Li(THF)(η1-N,η3-Ar-Giso)]. Deprotonation of PrisoH and Pip(GisoH)2 with K[N(SiMe3)2] gave the unsolvated polymer, [{K(η1-N,η6-Ar-Priso)}∞], and the solvated complex, [{K(THF)2}{Pip(Giso)2}{K(THF)3}], respectively.

Item ID: 29697
Item Type: Article (Research - C1)
ISSN: 1369-9261
Keywords: heterocyclic carbene analogs; coordination chemistry; group-13 metal(i); amidinate complexes; aluminum; lithium; ligand; carbodiimides; fragments; isomers
Funders: Australian Research Council (ARC), Leverhulme Trust , Erasmus Scheme of the European Union , Royal Society , US Air Force Asian Office of Aerospace Research and Development
Date Deposited: 02 Oct 2013 10:34
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030204 Main Group Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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