34675-93-9Relevant academic research and scientific papers
Synthesis and characterization of arene, mono-and dihydrido-arene, monohydrido-cyclopentadienyl, and phosphite complexes of molybdenum containing the tridentate ligand PhP (CH2CH2PPh2)2
Hammud, Hassan H.,George, T. Adrian,Kurk, David N.,Shoemaker, Richard K.
, p. 153 - 159 (2008/10/08)
The reduction of [MoCl3(TRI)], where TRI = PhP(CH2CH2PPh2)2, with sodium amalgam in benzene, toluene or anisole resulted in the formation of the corresponding [Mo(η6-arene) (TRI)] complex. Each complex displayed a reversible one-electron oxidation in the cyclic voltammogram at ～ - 1.0 V versus the ferrocenium/ferrocene couple at 0.0 V, corresponding to the oxidation of Mo(0) to Mo(1+). A second pseudo-reversible oxidation occurred at ～0.7 V more positive. Monoprotonation of the arene complexes with CF3COOH in THF resulted in the isolation of [Mo(H)(η6-arene)(TRI)][CF3COO] (δ(MoH) ～ - 6 ppm). In neat CF3COOH or HBF4, evidence of diprotonation of the arene complexes was observed in the 1H NMR spectra. Upon work-up, only the monoprotonated product was isolated. [Mo(TRI)(P(OMe)3)] was formed by the reduction of [MoCl3(TRI)] in the presence of a small excess of P(OMe)3. Attempts to prepare [Mo(TRI)(PMe3)3] by a similar method resulted in a product that readily absorbed N2 to form fac-[Mo(N2)(TRI)(PMe3)2]. Yellow [Mo(H)(η5-C5H5)(TRI)] was formed by (i) the reduction of [MoCl3(TRI)] with sodium amalgam in the presence of cyclopentadiene, or (ii) heating fac-[Mo(N2)(TRI)(PMe3)2] with cyclopentadiene in heptane, or (iii) heating trans-[Mo(N2)2(TRI)(PPh3)] with cyclopentadiene in THF.
Four-legged piano stool molybdenum(II) compounds without carbonyl ligands - 3? cyclopentadienyl and indenyl complexes containing the tridentate ligand Ph2PCH2CH2P(Ph)CH2CH 2PPh2(triphos) via reduction of molybdenum(III) precursors
Cole, Audrey A.,Mattamana, Sundeep P.,Poli, Rinaldo
, p. 2351 - 2361 (2008/10/09)
The carbonyl-free, half-sandwich molybdenum(II) complexes CpMoCl(triphos) (1) and IndMoX(triphos) [X = Cl (2); I (3); triphos = Ph2PCH2CH2P(Ph)CH2CH 2PPh2; Ind = η5-C7H9 or indenyl] have been synthesized by either reduction of CpMoCl2 in the presence of triphos or by reduction and transmetallation of MoX3(triphos) (X = Cl, I) with CpNa or IndNa. The spectroscopic properties indicate a saturated, 18-electron structure in each case. All compounds are susceptible to oxidation in chlorinated hydrocarbons and the oxidation of 1 has been studied in detail both chemically and electrochemically. Compound [1]+PF-6 has been obtained by oxidation of 1 with AgPF6, whereas the corresponding AlCl-4 salt has been prepared in a one-pot reaction from CpMoCl2, triphos and AlCl3. The structure of 1 has been confirmed by X-ray crystallography as a four-legged piano stool with an η5-cyclopentadienyl ring and a tridentate triphos ligand. Copyright
Synthesis and characterization of low valent complexes of molybdenum containing the tridentate ligand PhP(CH2CH2PPh2)2(TRI)
George, T. Adrian,Hammund, Hassan H.
, p. C1 - C3 (2007/10/03)
Reduction of with sodium amalgam in the presence of potential ligands results in the formation of a series of new complexes containing η3-TRI.These include 6-C6H5R)(TRI) (where R = H, Me, MeO), 5-C5H5)(H)(TRI)>, (where R = Me, Et), and fac-.Protonation of the arene complexes results in the formation of both mono- and diprotonated complexes.Keywords: Molybdenum; Phosphine; Phosphite; Dinitrogen; η6-Benzene complex; η6-Arene complex.
