TY - JOUR
T1 - Rapid Markovnikov Addition of HCl to a Pendant Alkyne: Evidence for a Quinoidal Cumulene
AU - Eaves, Samantha
AU - Hart, S.J.
AU - Whitwood, A.C.
AU - Yufit, D.S.
AU - Low, Paul
AU - Lynam, J.M.
PY - 2015/6/7
Y1 - 2015/6/7
N2 - Reaction of cis-[RuCl2(dppm)2]BF4 with TlBF4 and 1,4-diethynyl-benzenes results in the formation of the vinylidene cations trans-[Ru([double bond, length as m-dash]C[double bond, length as m-dash]CH–C6H2-2,5-R2-4-C[triple bond, length as m-dash]CH)Cl(dppm)2]+ (R = H, Me). Subsequent reaction with [NnBu4]Cl results in nucleophilic attack at the coordinated organic ligand, but not at the expected metal-bound carbon atom. Instead, trans-[Ru(C[triple bond, length as m-dash]C–C6H2-2,5-R2-4-CCl[double bond, length as m-dash]CH2)Cl(dppm)2] was generated which, when coupled with DFT calculations, provides evidence for an intermediate quinoidal cumulene complex.
AB - Reaction of cis-[RuCl2(dppm)2]BF4 with TlBF4 and 1,4-diethynyl-benzenes results in the formation of the vinylidene cations trans-[Ru([double bond, length as m-dash]C[double bond, length as m-dash]CH–C6H2-2,5-R2-4-C[triple bond, length as m-dash]CH)Cl(dppm)2]+ (R = H, Me). Subsequent reaction with [NnBu4]Cl results in nucleophilic attack at the coordinated organic ligand, but not at the expected metal-bound carbon atom. Instead, trans-[Ru(C[triple bond, length as m-dash]C–C6H2-2,5-R2-4-CCl[double bond, length as m-dash]CH2)Cl(dppm)2] was generated which, when coupled with DFT calculations, provides evidence for an intermediate quinoidal cumulene complex.
U2 - 10.1039/C4CC09696G
DO - 10.1039/C4CC09696G
M3 - Article
SN - 1359-7345
VL - 51
SP - 9362
EP - 9365
JO - Chemical Communications
JF - Chemical Communications
IS - 45
ER -