TY - JOUR
T1 - Dihydroperimidine-derived N-heterocyclic pincer carbene complexes via double C-H activation
AU - Hill, Anthony F.
AU - McQueen, Caitlin M.A.
PY - 2012/12/10
Y1 - 2012/12/10
N2 - The reactions of 1,8-diaminonaphthalene with paraformaldehyde and secondary phosphines (HPR2, R = Ph, Cy) directly afford N,N'- bis(phoshinomethyl)dihydroperimidines H2C(NCH2PR 2)2C10H6 (R = Ph (1a), Cy (1b)), the methylene group of which undergoes chelate-assisted double C-H activation with [RhCl(PPh3)3] to afford dihydroperimidine-derived N-heterocyclic pincer carbene (per-NHC) complexes [RhCl{=C(NCH 2PR2)2C10H6}] (R = Ph (2a), Cy (2b)). Insight into the mechanism of these C-H activation processes is provided by the reaction of 1b with [IrCl(CO)(PPh3)2] to provide the dihydroperimidinyl-hydrido complex [IrHCl(CO){CH(NCH 2PR2)2C10H6}] (3b), which in turn reacts with silver salts Ag[Y] to afford, via hydride abstraction and subsequent C-H activation, the per-NHC ligated salts [IrHCl(CO){=C(NCH 2PR2)2C10H6}] ([4b]Y, Y = PF6, SbF6, PO2F2).
AB - The reactions of 1,8-diaminonaphthalene with paraformaldehyde and secondary phosphines (HPR2, R = Ph, Cy) directly afford N,N'- bis(phoshinomethyl)dihydroperimidines H2C(NCH2PR 2)2C10H6 (R = Ph (1a), Cy (1b)), the methylene group of which undergoes chelate-assisted double C-H activation with [RhCl(PPh3)3] to afford dihydroperimidine-derived N-heterocyclic pincer carbene (per-NHC) complexes [RhCl{=C(NCH 2PR2)2C10H6}] (R = Ph (2a), Cy (2b)). Insight into the mechanism of these C-H activation processes is provided by the reaction of 1b with [IrCl(CO)(PPh3)2] to provide the dihydroperimidinyl-hydrido complex [IrHCl(CO){CH(NCH 2PR2)2C10H6}] (3b), which in turn reacts with silver salts Ag[Y] to afford, via hydride abstraction and subsequent C-H activation, the per-NHC ligated salts [IrHCl(CO){=C(NCH 2PR2)2C10H6}] ([4b]Y, Y = PF6, SbF6, PO2F2).
UR - http://www.scopus.com/inward/record.url?scp=84870862812&partnerID=8YFLogxK
U2 - 10.1021/om300897w
DO - 10.1021/om300897w
M3 - Article
SN - 0276-7333
VL - 31
SP - 8051
EP - 8054
JO - Organometallics
JF - Organometallics
IS - 23
ER -