TY - JOUR
T1 - The syntheses and structures of mono- and di-bromovinylidenes
AU - Brown, N.J.
AU - Fox, M.A.
AU - Smith, M.E.
AU - Yufit, D.S.
AU - Howard, J.A.K.
AU - Low, Paul
PY - 2009/12/1
Y1 - 2009/12/1
N2 - Reactions of metal acetylide complexes M(C≡CAr)(PP)Cp′ (M = Fe, Ru; Ar = C6H5, C6H4Me-4; PP = (PPh3)2, dppe; Cp′ = Cp, Cp*; not all combinations), or the analogous vinylidene, with cyanogen bromide yield monobromovinylidene complexes [M{C=C(Br)Ar}(PP)Cp′]+, isolated as PF6− salts. The trimethylsilyl-capped acetylides M(C≡CSiMe3)(PP)Cp′ react with cyanogen bromide to give [M(C=CBr2)(PP)Cp′]+, the first examples of metal complexes containing a terminal dihalovinylidene ligand, which can be isolated as the BF4− salts. Molecular structures of representative mono- and di-bromovinylidene complexes are reported, together with those of Ru(C≡CSiMe3)(PPh3)2Cp and Ru(C≡CSiMe3)(dppe)Cp*.
AB - Reactions of metal acetylide complexes M(C≡CAr)(PP)Cp′ (M = Fe, Ru; Ar = C6H5, C6H4Me-4; PP = (PPh3)2, dppe; Cp′ = Cp, Cp*; not all combinations), or the analogous vinylidene, with cyanogen bromide yield monobromovinylidene complexes [M{C=C(Br)Ar}(PP)Cp′]+, isolated as PF6− salts. The trimethylsilyl-capped acetylides M(C≡CSiMe3)(PP)Cp′ react with cyanogen bromide to give [M(C=CBr2)(PP)Cp′]+, the first examples of metal complexes containing a terminal dihalovinylidene ligand, which can be isolated as the BF4− salts. Molecular structures of representative mono- and di-bromovinylidene complexes are reported, together with those of Ru(C≡CSiMe3)(PPh3)2Cp and Ru(C≡CSiMe3)(dppe)Cp*.
U2 - 10.1016/j.jorganchem.2009.08.027
DO - 10.1016/j.jorganchem.2009.08.027
M3 - Article
SN - 0022-328X
VL - 694
SP - 4042
EP - 4048
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 25
ER -