Silver Complexes of a Novel Tripodal N-Heterocyclic Carbene Ligand: Evidence for Significant Metal-Carbene pi-Interaction

A novel N-heterocyclic tridentate polycarbene ligand has been synthesized and stabilized as its corresponding silver complex. An electronic structure investigation reveals significant pi-bonding interactions within the Ag-carbene unit of the [(TIMEMe)2Ag3]3+ cation. Thus, reaction of [1,1,1-tris(3-methylimidazolium-1-yl)methyl]ethane tribromide (1a; {[TIMEMe](Br)3}, prepd. via reaction of 1,1,1-tris(bromomethyl)ethane with N-methylimidazole) with NH4PF6 in MeOH gave [TIMEMe](PF6)3 (1b). Reaction of 1a and 1b with Ag2O in DMSO gave title compds., [(TIMEMe)2Ag3](Ag8Br14) (2a) and [(TIMEMe)2Ag3](PF6)3 (2b) resp. The crystal structures of 1a, 2a, and 2b were detd. and electronic structures via DFT calcns. were discussed. [on SciFinder (R)]


Published in:
Organometallics, 22, 4, 612-614
Year:
2003
Keywords:
Note:
CAN 138:221653 29-9 Organometallic and Organometalloidal Compounds Department of Chemistry and Biochemistry,University of California, San Diego,La Jolla,CA,USA. Journal 0276-7333 written in English. 501086-88-0P Role: CPS (Chemical process), PEP (Physical, engineering or chemical process), PRP (Properties), SPN (Synthetic preparation), PREP (Preparation), PROC (Process) (DFT mol. structure calcn.; prepn. and crystal and mol. structures of silver complexes of novel tripodal N-heterocyclic carbene ligand and evidence for significant metal-carbene pi-interaction); 501086-84-6P Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and crystal and mol. structures of silver complexes of novel tripodal N-heterocyclic carbene ligand and evidence for significant metal-carbene pi-interaction); 616-47-7 (N-Methylimidazole); 60111-68-4 (1,1,1-Tris(bromomethyl)ethane) Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. and crystal and mol. structures of silver complexes of novel tripodal N-heterocyclic carbene ligand and evidence for significant metal-carbene pi-interaction); 501086-86-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and crystal and mol. structures of silver complexes of novel tripodal N-heterocyclic carbene ligand and evidence for significant metal-carbene pi-interaction)
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