Evidence for a reactive (alkene)peroxoiridium(III) intermediate in the oxidation of an alkene complex with O2.
نویسندگان
چکیده
An (alkene)peroxoiridium(III) complex, [Ir(L)(cod)(O(2))] [where LH = PhN=C(NMe(2))NHPh and cod = 1,5-cyclooctadiene], was identified as an intermediate in the reaction of the Ir(I) precursor [Ir(L)(cod)] with O(2) and characterized by spectroscopic methods. Decay of the intermediate and further reaction with 1,5-cyclooctadiene produced 4-cycloocten-1-one.
منابع مشابه
Guanidinato and amidinato complexes of iridium(I): synthesis O<sub>2</sub> and S<sub>8</sub> reactivity, and (alkene)peroxo- and (alkene)persulfidoiridium(III) intermediates
A variety of mononuclear alkene complexes, [Ir{ArNC(NR2)NAr}(cod)], and dicarbonyl complexes, [Ir{ArNC(NR2)NAr}(CO)2] (where R = Me or Et; Ar = Ph, 4MeC6H4, 4-MeOC6H4, 2,6-Me2C6H3 or 2,6-Pr2C6H3; and cod = 1,5-cyclooctadiene), were synthesized from the neutral N,N-dialkyl-N′,N′′-diarylguanidines via deprotonation and transmetalation. These complexes were fully characterized by spectroscopic tec...
متن کاملFormation and reactivity of an (alkene)peroxoiridium(III) intermediate supported by an amidinato ligand.
An Ir(I) complex of an acetamidinato ligand was synthesized by reaction of N,N'-diphenylacetamidine, PhN[double bond, length as m-dash]C(Me)NHPh, with either MeLi and [{Ir(cod)}2(μ-Cl)2] or [{Ir(cod)}2(μ-OMe)2] and was characterized by X-ray crystallography as a mononuclear complex, [Ir{PhNC(Me)NPh}(cod)] (1; where cod = 1,5-cyclooctadiene). Reaction of 1 with CO afforded a dinuclear carbonyl c...
متن کاملCharge-transfer mediated photochemistry in alkene–O2 complexes
The photochemistry of a series of alkene–O2 complexes was studied in a supersonic expansion using a resonance enhanced multiphoton ionization probe of the O(P j) photoproduct at 226 nm. The relative yield of oxygen atoms from each complex was correlated to the ionization potential of the alkene species and indicates that initial excitation of an intermolecular charge-transfer state mediates the...
متن کاملCometabolic degradation of chlorinated alkenes by alkene monooxygenase in a propylene-grown Xanthobacter strain.
Propylene-grown Xanthobacter cells (strain Py2) degraded several chlorinated alkenes of environmental concern, including trichloroethylene, 1-chloroethylene (vinyl chloride), cis- and trans-1,2-dichloroethylene, 1,3-dichloropropylene, and 2,3-dichloropropylene. 1,1-Dichloroethylene was not degraded efficiently, while tetrachloroethylene was not degraded. The role of alkene monooxygenase in cata...
متن کاملStereoselective Formation of Substituted 1,3-Dioxolanes through a Three-Component Assembly during the Oxidation of Alkenes with Hypervalent Iodine(III).
Stereoselective formation of substituted 1,3-dioxolanes was achieved through an assembly of three components: alkene, carboxylic acid and silyl enol ether. The reaction proceeded via stereospecific generation of a 1,3-dioxolan-2-yl cation intermediate during oxidation of alkene substrates with hypervalent iodine. The stereoselective trapping of the cation intermediate with silyl enol ether comp...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemical communications
دوره 48 23 شماره
صفحات -
تاریخ انتشار 2012