TY - JOUR
T1 - Synthesis and properties of ferrocenyl allenylidene complexes
T2 - X-ray structure of [Ru(C=C=CHFc)(PPh3)2(η5-C 5H5)][PF6] CH2Cl2
AU - Byrne, Lindsay T.
AU - Koutsantonis, George A.
AU - Sanford, Vanessa
AU - Selegue, John P.
AU - Schauer, Phil A.
AU - Iyer, Ramnath S.
PY - 2010/3/8
Y1 - 2010/3/8
N2 - Reactions of the transition metal halide complexes [MXL2(Cp)] (M = Fe, X = I, L2 = dppe; M = Ru, X = Cl, L = PPh3; M = Os, X = Br, L = PPh3; Cp = 77-C5H5) with the alkynol HC=CCH(OH)(Fc) (1) (Fc = ferrocenyl) in the presence of TlBF4 gave the monosubstituted allenylidene complexes [M(C=C=CHFc)L 2(Cp)][BF4] (2a: M = Ru, L = PPh3; 3: M = Fe, L2 = dppe; 4: M = Os, L = PPh3). Similarly, the reaction of 1 with [RuCl(PPh3)2(Cp)] and NH4PF 6 in methanol gave [Ru(C=C=CHFc)(PPh3)2(Cp)] [PF6] (2b). These highly colored compounds were characterized by spectroscopic and electrochemical techniques and in the case of 2b by a single-crystal X-ray structure determination. Cyclic voltammetry in MeCN in the presence of ["Bu4N][ClO4] at 100 mV-s-1 shows a reversible ferrocenyl-based one-electron oxidation, in addition to irreversible oxidation and reduction processes. The NMR spectra of 2b show complex behavior at low temperature, attributed to temperature-dependent chemical shifts and correlated motions of the allenylidene ligand and the ferrocenyl substituent.
AB - Reactions of the transition metal halide complexes [MXL2(Cp)] (M = Fe, X = I, L2 = dppe; M = Ru, X = Cl, L = PPh3; M = Os, X = Br, L = PPh3; Cp = 77-C5H5) with the alkynol HC=CCH(OH)(Fc) (1) (Fc = ferrocenyl) in the presence of TlBF4 gave the monosubstituted allenylidene complexes [M(C=C=CHFc)L 2(Cp)][BF4] (2a: M = Ru, L = PPh3; 3: M = Fe, L2 = dppe; 4: M = Os, L = PPh3). Similarly, the reaction of 1 with [RuCl(PPh3)2(Cp)] and NH4PF 6 in methanol gave [Ru(C=C=CHFc)(PPh3)2(Cp)] [PF6] (2b). These highly colored compounds were characterized by spectroscopic and electrochemical techniques and in the case of 2b by a single-crystal X-ray structure determination. Cyclic voltammetry in MeCN in the presence of ["Bu4N][ClO4] at 100 mV-s-1 shows a reversible ferrocenyl-based one-electron oxidation, in addition to irreversible oxidation and reduction processes. The NMR spectra of 2b show complex behavior at low temperature, attributed to temperature-dependent chemical shifts and correlated motions of the allenylidene ligand and the ferrocenyl substituent.
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U2 - 10.1021/om9010214
DO - 10.1021/om9010214
M3 - Article
AN - SCOPUS:77749233946
SN - 0276-7333
VL - 29
SP - 1199
EP - 1209
JO - Organometallics
JF - Organometallics
IS - 5
ER -