000222216 001__ 222216
000222216 005__ 20181203024412.0
000222216 0247_ $$2doi$$a10.1002/chem.201602267
000222216 022__ $$a0947-6539
000222216 02470 $$2ISI$$a000382925000035
000222216 037__ $$aARTICLE
000222216 245__ $$aAlcohol-Induced C-N Bond Cleavage of Cyclometalated N-Heterocyclic Carbene Ligands with a Methylene-Linked Pendant Imidazolium Ring
000222216 260__ $$bWiley-Blackwell$$c2016$$aWeinheim
000222216 269__ $$a2016
000222216 300__ $$a7
000222216 336__ $$aJournal Articles
000222216 520__ $$aReaction of the pentamethylcyclopentadienyl rhodium iodide dimer [Cp*RhI2](2) with 1,1'-diphenyl-3,3'-methylenediimidazolium diiodide in non-alcohol solvents, in the presence of base, led to the formation of bis-carbene complex [Cp*Rh(bis-NHC)I] I (bis-NHC=1,1'-diphenyl-4,4'-methylenediimidazoline-5,5'-diylidene). In contrast, when employing alcohols as the solvent in the same reaction, cleavage of a methylene C-N bond is observed, affording ether-functionalized (cyclometalated) carbene ligands coordinated to the metal center and the concomitant formation of complexes with a coordinated imidazole ligand. Studies employing other 1,1'-diimidazolium salts indicate that the cyclometalation step is a prerequisite for the activation/scission of the C-N bond and, based on additional experimental data, a S(N)2 mechanism for the reaction is tentatively proposed.
000222216 6531_ $$acarbene complexes
000222216 6531_ $$aC-N bond cleavage
000222216 6531_ $$acyclometalation
000222216 6531_ $$aimidazolium salts
000222216 6531_ $$aN-heterocyclic carbenes
000222216 700__ $$uEcole Polytech Fed Lausanne, Inst Sci & Ingn Chim, CH-1015 Lausanne, Switzerland$$aZhong, Wei
000222216 700__ $$0240012$$g153598$$uEcole Polytech Fed Lausanne, Inst Sci & Ingn Chim, CH-1015 Lausanne, Switzerland$$aFei, Zhaofu
000222216 700__ $$0240189$$g148592$$uEcole Polytech Fed Lausanne, Inst Sci & Ingn Chim, CH-1015 Lausanne, Switzerland$$aScopelliti, Rosario
000222216 700__ $$aDyson, Paul J.$$uEcole Polytech Fed Lausanne, Inst Sci & Ingn Chim, CH-1015 Lausanne, Switzerland$$g149418$$0240015
000222216 773__ $$j22$$tChemistry-A European Journal$$k34$$q12138-12144
000222216 909C0 $$xU9$$0252010$$pLCOM
000222216 909CO $$pSB$$particle$$ooai:infoscience.tind.io:222216
000222216 917Z8 $$x135992
000222216 937__ $$aEPFL-ARTICLE-222216
000222216 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000222216 980__ $$aARTICLE