223527-31-9Relevant academic research and scientific papers
Kinetic studies of the alkylation of metal cyanide complexes: M(CO)x(L)5-xCN (M = Mn, Re) and CpM′(CO)x(L)2-xCN (M′ = Fe, Ru)
Cardoza, Laurie A.,Angelici, Robert J.
, p. 1708 - 1712 (1999)
Reaction rates for the alkylation of Mn(CO)(dppm)2CN (dppm = PPh2CH2PPh2), Mn(CO)2(tripod)CN [tripod = (PPh2CH2)3CCH3], Re(CO)3(dppm)CN, (η6-C6Me6)Mn(CO)2CN, CpFe(dppe)CN (dppe = PPh2CH2CH2PPh2), CpRu(dppe)CN, and CpRu(CO)(PPh3)CN with methyl 4-nitrobenzenesulfonate (MeONs) to produce complexes of the type [LnM-CNMe]+ -ONs were investigated in 1,2-dichloroethane (DCE) at 30.0 °C. The reactions are first order in both the complex and the alkylating agent, which is consistent with a mechanism that involves nucleophilic attack of the cyanide nitrogen on the methyl of the MeONs. The second-order rate constants (k2) correlate approximately with the stretching frequency of the cyanide ligand v(CN) in the complexes. There is a somewhat better correlation between v(CN) of the CNCH3 ligands in the products and k2. There is also a good correlation between the rate constant (k2) and the calculated force constant (KCO) for the v(CO) vibrational mode of the analogous [LnM-CO]+ complex. These correlations appear to be useful for predicting nucleophilicities of metal cyanide complexes of different metals, in different oxidation states, and with ligands exhibiting a range of electronic and steric properties.
