Carnegie Mellon University

Terrence J Collins

Scott W Gordon-Wylie

Colin P Horwitz

William Chadwick Ellis

Genoa Rose Warner

Matthew Alan DeNardo

Yogesh Somasundar

Riddhi Roy

Newell R Washburn

An especially robust compound and its derivative metal complexes that are approximately one hundred-fold superior in catalytic performance to the previously invented TAML analogs is provided having the formula (I) wherein Y, Y, Yand Yare oxidation resistant groups which are the same or different and which form 5- or 6-membered rings with a metal, M, when bound to D; at least one Y incorporates a group that is significantly more stable towards nucleophilic attack than the organic amides of TAML activators; D is a metal complexing donor atom, preferably N; each X is a position for addition of a labile Lewis acidic substituent such as (i) H, deuterium, (ii) Li, Na, K, alkali metals, (iii) alkaline earth metals, transition metals, rare earth metals, which may be bound to one or more than one D, (iv) or is unoccupied with the resulting negative charge being balanced by a nonbonded counter-action; at least one Y may contain a site that is labile to acid dissociation, providing a mechanism for shortening complex lifetime. The new complexes deliver catalytic performances that promise to revolutionize multiple oxidation technology spaces including water purification.

Far superior oxidation catalysts based on macrocyclic compounds

An especially robust compound and its derivative metal complexes that are approximately one hundred-fold superior in catalytic performance to the previously invented TAML analogs is provided having the formula: wherein

The invention provides a novel composition and method for removing or reducing levels of recalcitrant constituents from an effluent, such as lignin chromophores, AOX species, such as chlorinated phenols, dioxins, dibenzofurans, biphenyls, and high molecular weight material produced in the pulp and paper bleaching operations which includes using a composition comprised of (a) an amount of a source of an oxidant effective for oxidizing and thereby reducing the levels of such constituents and (b) an oxidatively stable oxidant activator having the structure

Metal ligand containing bleaching compositions

The invention provides a novel composition and method for removing or reducing levels of recalcitrant constituents from an effluent, such as lignin chromophores, AOX species, such as chlorinated phenols, dioxins, dibenzofurans, biphenyls, and high molecular weight material produced in the pulp and paper bleaching operations which includes using a composition comprised of (a) an amount of a source of an oxidant effective for oxidizing and thereby reducing the levels of such constituents and (b) an oxidatively stable oxidant activator having the structure ##STR1## wherein Y.sub.1, Y.sub.3 and Y.sub.4 each represent a bridging group having zero, one, two or three carbon containing nodes for substitution, and Y.sub.2 is a bridging group having at least one carbon containing node for substitution, each said node containing a C(R), C(R.sub.1)(R.sub.2), or a C(R).sub.2 unit and each R substituent is the same or different from the remaining R substituents; M is a transition metal with oxidation states of I, II, III, IV, V, VI, VII or VIII or selected from Groups 3, 4, 5, 6, 7, 8, 9, 10 and 11 of the Periodic Table of the Elements; and Q is any counterion which would balance the charge of the compound on a stoichiometric basis.

A robust chelate complex is provided having the formula: ##STR1## wherein: M is a metal, preferably a transition metal; Z is an anionic donor atom, three of which are nitrogen, and the other is oxygen; L.sub.1 is a labile ligand;

Long-lived homogenous oxidation catalysts

The invention provides a novel bleaching composition comprising:

A robust compound is provided having the formula: ##STR1## wherein Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 are oxidation resistant groups which are the same or different and which form 5- or 6-membered rings with a metal, M, when bound to D. D is a metal complexing donor atom, O or N. Each X is a position for addition of a substituent and, when D is N, each position is (i) not occupied such that a double bond is formed between D and an atom adjacent to D, or (ii) is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, alkoxy, phenoxy, halogen, halogenated alkyl, halogenated aryl, halogenated alkenyl, halogenated alkynyl, perhaloalkyl, perhaloaryl, a substituted or unsubstituted cycloalkyl ring, a substituted or unsubstituted cycloalkenyl ring, a substituted or unsubstituted saturated heterocyclic ring, a substituted or unsubstituted unsaturated heterocyclic ring, and at least one X is hydrogen, and when D is O, the position is not occupied.

Long-lived homogenous amide containing macrocyclic compounds

New synthetic methods for the preparation of macrocyclic amido-N donor ligands are provided. The primary method of the present invention involves in general only two synthetic steps. In the first step, an .alpha. or .beta. amino carboxylic acid is allowed to react with an optimal (approximately stoichiometric) amount of an activated malonate or oxalate derivative with mild heating. Upon completion of the double coupling reaction, hydrolysis of the reaction mixture yields a diamide containing intermediate (a macro linker). In the second step, stoichiometric amounts of a diamine, preferably an orthophenylene diamine, are added to the macro linker intermediate in the presence of a coupling agent and heat. This second double coupling reaction, is allowed to proceed for a period of time sufficient to produce a macrocyclic tetraamido compound. The substituent groups on the .alpha. or .beta. amino carboxylic acid, the malonate, and the aryl diamine may all be selectively varied so that the resulting tetraamido macrocycle can be tailored to specific desired end uses. The macrocyclic tetraamide ligand may then be complexed with a metal, such as a transition metal, and preferably the middle and later transition metals, to form a robust chelate complex suitable for catalyzing oxidation reactions.

Synthesis of macrocyclic tetraamido-N ligands

The invention provides a novel composition for bleaching cellulose based materials, such as wood pulp and paper comprising:

A robust chelate complex is provided having the formula: ##STR1## wherein M is a metal, preferably a transition metal; Z is an anionic donor atom, at least three of which are nitrogen and the other is preferably nitrogen or oxygen; L.sub.1 is a labile ligand;

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Pittsburgh, PA, United States of America

Terrence J Collins