Hydrogen oxidation catalysis by a nickel diphosphine complex with pendant tert-butyl amines.
نویسندگان
چکیده
A bis-diphosphine nickel complex with tert-butyl functionalized pendant amines [Ni(P(Cy)(2)N(t-Bu)(2))(2)](2+) has been synthesized. It is a highly active electrocatalyst for the oxidation of hydrogen in the presence of base. The turnover rate of 50 s(-1) under 1.0 atm H(2) at a potential of -0.77 V vs. the ferrocene couple is 5 times faster than the rate reported heretofore for any other synthetic molecular H(2) oxidation catalyst.
منابع مشابه
Two pathways for electrocatalytic oxidation of hydrogen by a nickel bis(diphosphine) complex with pendant amines in the second coordination sphere.
A nickel bis(diphosphine) complex containing pendant amines in the second coordination sphere, [Ni(P(Cy)2N(t-Bu)2)2](BF4)2 (P(Cy)2N(t-Bu)2 = 1,5-di(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane), is an electrocatalyst for hydrogen oxidation. The addition of hydrogen to the Ni(II) complex gives three isomers of the doubly protonated Ni(0) complex [Ni(P(Cy)2N(t-Bu)2H)2](BF4)2. U...
متن کاملReduction of oxygen catalyzed by nickel diphosphine complexes with positioned pendant amines.
Nickel(II) bis(diphosphine) complexes that contain positioned bases in the second coordination sphere have been found to catalyze the reduction of O(2) with H(2) to selectively form water. The complexes also serve as electrocatalysts for the reduction of O(2) with the addition of a weak acid. In contrast, a closely related nickel diphosphine complex without the positioned bases is catalytically...
متن کاملOxidation of secondary amines catalyzed by dirhodium caprolactamate.
The dirhodium caprolactamate [Rh(2)(cap)(4)] catalyzed oxidation of secondary amines to imines by tert-butyl hydroperoxide (TBHP) occurs with high chemo- and regioselectivity.
متن کاملCharacterization and reactivity of a terminal nickel(III)-oxygen adduct.
High-valent terminal metal-oxygen adducts are hypothesized to be the potent oxidizing reactants in late transition metal oxidation catalysis. In particular, examples of high-valent terminal nickel-oxygen adducts are scarce, meaning there is a dearth in the understanding of such oxidants. A monoanionic Ni(II)-bicarbonate complex has been found to react in a 1:1 ratio with the one-electron oxidan...
متن کاملMechanistic insights into catalytic h(2) oxidation by ni complexes containing a diphosphine ligand with a positioned amine base.
The mixed-ligand complex [Ni(dppp)(P(Ph)(2)N(Bz)(2))](BF(4))(2), 3, (where P(Ph)(2)N(Bz)(2) is 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane and dppp is 1,3-bis(diphenylphosphino)propane) has been synthesized. Treatment of this complex with H(2) and triethylamine results in the formation of the Ni(0) complex, Ni(dppp)(P(Ph)(2)N(Bz)(2)), 4, whose structure has been determined by a...
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 46 45 شماره
صفحات -
تاریخ انتشار 2010