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Neutral and Cationic Fluorinated N-Heterocyclic Carbene Complexes of Rhodium and Iridium


Reference:

Burling, S., Mahon, M. F., Reade, S. P. and Whittlesey, M. K., 2006. Neutral and Cationic Fluorinated N-Heterocyclic Carbene Complexes of Rhodium and Iridium. Organometallics, 25 (15), pp. 3761-3767.

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Abstract

Transmetalation of the structurally characterized silver N-heterocyclic carbene (NHC) salt [Ag(IpFMe)2]+ (1, IpFMe = 1-pentafluorobenzyl-3-methylimidazol-2-ylidene) to [Rh(COD)Cl]2 affords Rh(IpFMe)(COD)Cl (2) in 95% yield. The analogous neutral iridium complex, Ir(IpFMe)(COD)Br (5), may be formed upon elimination of MeOH from [Ir(COD)(OMe)]2 in the reaction with 1-pentafluorobenzyl-3-methylimidazolium bromide in 47% yield. Thermolysis of [Ag(IpFMe)2]+ with either 5 or [Ir(COD)Cl]2 yields the cationic bis-NHC complex [Ir(IpFMe)2(COD)](AgX2) (X = Cl, Br), which exists as a mixt. of conformers in soln. [Ir(IpFMe)2(COD)](AgBr2) (6) was isolated in 55% yield by reaction of 1 with 5. Addn. of CO or AgOTf to 2 gives Rh(IpFMe)(CO)2Cl (3) in 72% yield and Rh(IpFMe)(COD)(OTf) (4) in 85% yield, resp. The mol. structures of compds. 1-6 have been detd. by x-ray crystallog.

Details

Item Type Articles
CreatorsBurling, S., Mahon, M. F., Reade, S. P. and Whittlesey, M. K.
Uncontrolled Keywordsiridium cyclooctadienyl fluorinated bisimidazolylidene carbene complex prepn, o-c6f5 interactions, through-space interaction (silver-silver, rhodium, bond length (carbon-metal, transition metal complexes role, prepn. and properties of neutral and cationic fluorinated n-heterocyclic carbene complexes of rhodium and iridium), transmetalation (prepn. and properties of neutral and cationic fluorinated n-heterocyclic carbene complexes of rhodium and iridium), crystal structure, rhodium fluorinated bisimidazolylidene carbene complex cyclooctadienyl triflate carbonyl prepn, crystal structure pentafluorobenzyl methylimidazol silver cyclooctadienyl carbonyl rhodium iridium, coordination number (four, mol structure silver rhodium iridium pentafluorobenzyl methylimidazol cyclooctadienyl carbonyl, ract (reactant or reagent) (carbene complexes, prp (properties), rct (reactant), prep (preparation), conformers, molecular rotation (lack of rotation about the rh-carbene bond, ract (reactant or reagent) (transition metal complexes, neutral cationic rhodium iridium fluorinated imidazolylidene carbene complex prepn, molecular structure (of neutral and cationic fluorinated n-heterocyclic carbene complexes of rhodium and iridium), carbene complexes role, silver pentafluorobenzyl methylimidazol carbene complex transmetalation cyclooctadienyl rhodium iridium, spn (synthetic preparation)
DepartmentsFaculty of Science > Chemistry
RefereedYes
StatusPublished
ID Code4729

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