176507-34-9Relevant academic research and scientific papers
Stable mononuclear, 17-electron molybdenum(III) carbonyl complexes. Synthesis, structure, thermal decomposition, and Cl- addition reactions
Fettinger, James C.,Keogh, D. Webster,Poli, Rinaldo
, p. 3617 - 3625 (1996)
The first examples of stable, mononuclear 17-electron carbonyl complexes of Mo(III) have been synthesized, isolated, and characterized by IR and EPR spectroscopy. Oxidation of Cp*MoCl(CO)(PMe3)2 (1; E( 1/2 ) = -0.48 V vs Fc/Fc+), Cp*MoCl(CO)(dppe) (2; E( 1/2 ) = -0.44 V), and CpMoCl(CO)(dppe) (3; E( 1/2 ) = -0.25 V) with Fc+PF6- yields [1]PF6, [2]PF6, and [3]PF6, respectively. The IR stretching vibration of the 17-electron oxidation products are 136-153 cm-1 blue-shifted with respect to the corresponding stretching vibrations of the parent Mo(II) compounds. The room temperature EPR spectra show observable coupling to the Mo and P nuclei and indicate a trans geometry for 1+ and a cis geometry for 2+ and 3+. The four-legged piano stool geometry of 2+ with the phosphines atoms in relative cis positions has been confirmed by a single-crystal X-ray analysis. The X-ray data for [2]PF6·THF are the following: monoclinic, P21/n, a = 13.7394(14) A?, 6 = 20.421(2) A?, c = 14.857(2) A?, β = 99.119(8)°, V = 4115.8(8) A?3, Z = 4 D(x) = 1.469 g·cm-3, λ(Mo Kα) =0.71073 A?, μ (Mo Kα) = 0.562 mm-1, R(F) = 4.59%, R(wF2) = 10.77% for 4299 data with E(o) > 4σ(F(o)) The thermal stability of the cations decreases with increasing carbonyl stretching frequencies in the order 1+ > 2+ >> 3+. The decarbonylated product of thermolysis of 3+, [CpMoClF(dppe)(MeCN)]+PF6-, [4]PF6, which is believed to arise via a 15-electron [CpMoCl(dppe)]+ intermediate, has been isolated and characterized by 1H, 31P, and 19F NMR spectroscopies as well as a single-crystal X-ray analysis. The structure of 4+ shows a distorted pseudooctahedral geometry with the Cp ring and the F atom occupying the two axial coordination sites and the two phosphine atoms of the dppe occupying two cis equatorial sites. The data for [4]PF6·MeCN are as follows: monoclinic, P21/n, a = 13.160(2) A?, b = 10.942(2) A?, c = 25.010(3) A?, β = 95.225(10)°, V = 3586.4(9) A?3, Z = 4, D(x) = 1.557 g·cm-3, μ(Mo Kα) = 0.71073 A?, R(F) = 4.11% R(wF2) = 11.81% for 5964 data with F(o) > 4σ(F(o)). The nucleophilic addition of Cl- to 1+, 2+, or 3+ is followed by redox processes to afford mixtures of the parent Mo(II) carbonyl complexes 1-3 and Mo(IV) or Mo(V) products, depending on the nature of the ligands. The mechanism of these reactions has been elucidated through parallel chemical and electrochemical studies.
Synthesis, redox chemistry, and electronic structure of the alkynyl cyclopentadienyl molybdenum complexes [Mo(C≡CR)(CO)(L2)Cp] n+ (n = 0 or 1; R = Ph or C6H4-4-Me, L 2 = Ph2PCH2C
Roberts, Hannah N.,Brown, Neil J.,Edge, Ruth,Lewin, Ross,Collison, David,Low, Paul J.,Whiteley, Mark W.
, p. 3763 - 3778 (2011/08/09)
Two series of bis-phosphine-substituted cyclopentadienyl molybdenum alkynyl complexes, [Mo(C≡CR)(CO)(dppe)Cp] and trans-[Mo(C≡CR)(CO)(PMe 3)2Cp] (R = Ph or C6H4-4-Me, dppe = Ph2PCH2CH2
