Cationic 5-phosphonio-substituted N-heterocyclic carbenes

2-Phosphanyl-substituted imidazolium salts 2-PIR2(4,5-CE-Im)[OTf] (9a,b[OTf]) (4,5-Cl-Im = 4,5-dichloro-1,3-bis(2,6-di-isopropylphenyI)- midazolium) (a: R = Cy, b: R = Ph) are prepared from the reaction of R2PCl (R = Cy, Ph) with NHC 8 (4,5-dichloro-1,3-bis(2,6-di-isopropylphenyl)-imidazolin-2ylidene) in the presence of Me3SiOTf. 5-Phospanyl-substituted imidazolium salts 5-PR2(2,4-Cl-lm)[OTf] (10a,1:[OTf]) are obtained in quantitative yield when a slight excess of the NHC 8 is used. 5-Phosphonio-substituted imidazolium salts 5-PR2Me(2,4-Cl-Im)[OTf](2) (14a,b[OTf](2)) and 5-PR2F(2,4-Cl-Im)[OTf](2) (1.6a,b[OTf](2)) result from methylation reaction or oxidation of 10a,b[OTf] with XeF2 and subsequent fluoride abstraction. According to our quantum chemical studies the CR atom at the 2-position at the imidazolium ring of dication 14b(2+) carries a slightly positive charge and is therefore accessible for nucleophilic attack. Accordingly, the reaction of 14a,b[OTf](2) and 16a,b[OTf](2) with R3P (R = Cy, Ph) affords cationic 5-phosphonio-substituted NHCs 5-PR2Me(4-Cl-NHC)[OTf] (17a,b[OTf]) and 5-PR2F(4-Cl-NHC) [OTf] (18a,b[OTf]) Via a S(N)2(Cl)-type reaction. A series of transition metal complexes such as [AuCl(5-PPh2Me(4-CE-NHC))][OTf] (19[OTf]), [CuBr(5-PPh2Me(4-CE-NHC))][OTf] (20[OTf]), [AuCl(5-PPh2F(4-Cl-NHC))[OTf] (21[OTf]) and [RhCl(cod)(5-PPh2Me(4-Cl-NHC))][OTf] (23[0Tf]) are prepared to prove the coordination abilities of carbenes 17b[OTf] and 18b[OTf]. The isolation of a rare example of a tricationic bis-carbene silver complex [Ag(5-PPh2Me(4-Cl-NHC))(2)][OTf](3) (22[OTf](3)) is achieved by reacting 14b[OTf] with Cy3P in the presence of AgOTf. NHC 17b[OTf] represents a very effective dehydrocoupling reagent for secondary (R2PH, R = Ph, Cy, Bu-1) and primary (RPH2, R = Ph, Cy) phosphanes to give diphosphanes of type R4P2 (R = Ph, Cy, Bu-1) and oligophosphanes R4P4, R5P5 (R = Ph, Cy), respectively. Methylation of 17b(+) and subsequent deprotonation reaction with LDA affords the cationic NHO (N-heterocyclic olefin) 35(+) of which the gold complex 36(+) is readily accessible Via the reaction with AuCl(tht).