1005-93-2Relevant articles and documents
Oxygen atom insertion into iron(II) phenyl and methyl bonds: A key step for catalytic hydrocarbon functionalization
Mei, Jiajun,Pardue, Daniel B.,Kalman, Steven E.,Gunnoe, T. Brent,Cundari, Thomas R.,Sabat, Michal
, p. 5597 - 5605 (2014)
Oxy-functionalization of metal-alkyl and ?aryl bonds is a key step in potential hydrocarbon oxidation catalysis. However, well-defined examples of M-R to ROH conversion are rare, especially for first-row transition metals. CpFe(CO)(NCMe)Ph reacts with oxygen or hydrogen peroxide to produce benzoic acid. Removing CO from the CpFe(L)(L')Ph framework allows simple oxygen atom insertion into the Fe-Ph bond. CpFe(P(OCH2)3CEt)2Ph reacts with Me3NO in THF to produce PhOH in high yield when Bronsted acids are added. Studies show that light promotes P(OCH2)3CEt dissociation from CpFe(P(OCH2)3CEt)2Ph, which facilitates the conversion to PhOH. The methyl analogue CpFe[P(OCH2)3CEt]2Me reacts with oxidants to produce MeOH.
Synthesis of some alkyl phosphite complexes of platinum and their structural and spectral characterization
Solar, José M.,Rogers, Robin D.,Mason, W. Roy
, p. 373 - 377 (2008/10/08)
In order to explain why Pt(II) products were frequently observed, the synthetic procedure for Pt(0) alkyl phosphite complexes has been reexamined. According to the procedure the Pt(0) complexes [Pt(P(OEt)3)4], [Pt(P(OMe)3)4], and [Pt(ETPB)4] (ETPB = 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane) are formed initially by ligand reduction of PtCl42- accompanied by Cl- displacement. Subsequently, the Pt(0) complexes are found to undergo a reoxidation to Pt(II) if O2 is not excluded from the reaction mixture. The oxidation is accelerated by H+, but the nature of the Pt(II) product depends on the counterion. When [Pt(P(OEt)3)4] in alcoholic solution is treated with HClO4 and the solution saturated with air, [Pt(P(OEt)3)4](ClO4)2 can be isolated. In the presence of HCl, [Pt(P(OR)3)4] is converted to [Pt(P(OH)(OR)2)2(P(O)(OR)2)2] for R = Et or Me. These latter complexes contain four equivalent P atoms by 31P NMR and exhibit a low-field proton resonance (δ 16.5 (Me4Si) for Me and δ 16.6 (Me4Si) for Et) assigned to bridging hydrogens linking the (RO)2POH and (RO)2PO- ligands together in the complex. The structure of [Pt(P(OH)(OMe)2)2(P(O)(OMe)2)2] has been determined by X-ray diffraction techniques. It crystallizes in the monoclinic space group P21/c with unit cell parameters a = 7.147 (1) A?, b = 15.204 (2) A?, c = 10.680 (4) A?, β = 116.53 (2)°, and Dcalcd = 2.02 g cm-3 for Z = 2. The Pt atom resides on a crystallographic center of inversion and is bonded in a square-planar geometry to the four P atoms. The two unique P ligands are equivalent, bridged by a symmetric O?H?O hydrogen bond.