41753-77-9Relevant academic research and scientific papers
Oxygen atom transfer to metal carbonyls. Kinetics and mechanism of CO substitution reactions of M3(CO)11L (M = Fe, Ru, Os) in the presence of (CH3)3NO
Shen, Jian-Kun,Gao, Yi-Ci,Shi, Qi-Zhen,Basolo, Fred
, p. 4236 - 4239 (2008/10/08)
The rates and activation parameters are reported for CO-substitution reactions of M3(CO)11L (M = Fe, L = P(OEt)3, P(OMe)3; M = Ru, Os, L = P(OEt)3, P(OMe)3, P(n-Bu)3, PPh3, AsPh3, SbPh3) in the presence of (CH3)3NO. The rates of reaction are second order, first order in (CH3)3NO concentration, first order in M3(CO)11L concentration, and zero order in entering ligand concentration. For phosphite derivatives, the relative rates are M3(CO)11P(OMe)3 > M3(CO)11P(OEt)3. For other ligand-substituted complexes, the rates of reaction increase with increasing stretching frequency of the CO bands in the IR spectra. The mechanism involved appears to be similar to that proposed earlier of attack by the O atom of (CH3)3NO on a C atom of a CO coordinated to an unsubstituted metal atom. The unexpected slow rates for the reactions of M3(CO)11P(OR)3 are discussed in terms of shorter M-M bond distances in the cluster.
Substitution Kinetics of and
Dahlinger, Karl,Poe, Anthony J.,Sayal, Pardeep K.,Sekhar, Vasu C.
, p. 2145 - 2148 (2007/10/02)
The kinetics of reactions of and with P- or As-donor ligands in p-xylene or toluene have been studied and shown to be characteristic of reversible dissociative processes.In both cases MeCN is ca. 10 times more nucleophilic towards the reactive intermediate than is PPh3.Activation parameters confirm the weakness of the Os-NCMe bonds and suggest that loss of the first MeCN from may be a concerted process in which a 'sideways on' bridging CO replaces the leaving MeCN.The strength of bridge bonding can be estimated to be >= 30kJmol-1.
