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Terrence Collins
  • Pittsburgh, Pennsylvania, United States

Terrence Collins

  • A champion of green science, Terry Collins is widely recognized internationally for his invention of a new class of o... moreedit
Abstract X-ray crystal structure analysis of [Ru(η 2 -CS 2 Me)(CO) 2 (PPh 3 ) 2 ]ClO 4 reveals that the dithioester function is co-ordinated through carbon and the un-methylated sulphur atom; the chelate ring is opened by introduction of... more
Abstract X-ray crystal structure analysis of [Ru(η 2 -CS 2 Me)(CO) 2 (PPh 3 ) 2 ]ClO 4 reveals that the dithioester function is co-ordinated through carbon and the un-methylated sulphur atom; the chelate ring is opened by introduction of bidentate diethyldithiocarbamate and the resulting monodentate dithioester reacts rapidly with acids producing [Ru(η 2 -S 2 CNEt 2 )(CS)(CO)(PPh 3 ) 2 ] + and with MeI forming [Ru(η 2 -S 2 CNEt 2 ){(C(SMe) 2 }(CO)(PPh 3 ) 2 ] + .
Abstract The thiocarboxamido-thiocarbonyl cation, [Os(n 2 -SCNMeptolyl)(CS)(CO)(PPh 3 ) 2 ] + , upon reaction with NaBH 4 , forms Os(CS 2 C NMeptolyl)H(CO)(PPh 3 ) 2 through an inter-ligand reaction; x-ray crystal structure analysis of... more
Abstract The thiocarboxamido-thiocarbonyl cation, [Os(n 2 -SCNMeptolyl)(CS)(CO)(PPh 3 ) 2 ] + , upon reaction with NaBH 4 , forms Os(CS 2 C NMeptolyl)H(CO)(PPh 3 ) 2 through an inter-ligand reaction; x-ray crystal structure analysis of Os(CS 2 C NMeptolyl)H(CO)(PPh 3 ) 2 confirms the presence of a four-membered metallocycle and further reaction with MeI produces what is formally a chelate di-carbene ligand in [ Os(C(SMe)SC NMeptolyl)H(CO)(PPh 3 ) 2 ] + .
... 1967, 730. (20) Tyler, DR; Levenson, R. A,; Gray, HB J. Am. Chem. SOC. ... 7338. (1 9) Alfred P. Sloan Research Fellow, 1986-1988; Dreyfus Teacher-Scholar, 1 w6-1 wn I,-" I,,". The Chemical... more
... 1967, 730. (20) Tyler, DR; Levenson, R. A,; Gray, HB J. Am. Chem. SOC. ... 7338. (1 9) Alfred P. Sloan Research Fellow, 1986-1988; Dreyfus Teacher-Scholar, 1 w6-1 wn I,-" I,,". The Chemical Laboratories'* Claudia J. Barner California Institute of Technology Terrence J. Collins ...
7 minutes HPLC was used to track the reaction via time. Standards of both the amine and the ketone were run individually to determine the corresponding retention times. Calibration curves were made for each standard based on the... more
7 minutes HPLC was used to track the reaction via time. Standards of both the amine and the ketone were run individually to determine the corresponding retention times. Calibration curves were made for each standard based on the integration of the peaks. These calibration curves were used to determine the molar amounts of both ketone formation and amine loss during the TAML reactions. LC-MS data confirmed the retention times of both the amine and ketone. HPLC HPLC-MS
Research Interests:
Degradation of two textile dyes, C.I.Acid Orange 7 (Orange II) and C.I. Reactive Red 2 (Procion Red MX-5B) bound to silica gel and cellulose by hydrogen peroxide catalyzed by Fe (III) complexed to Tetra-Amido Macrocyclic Ligands (Fe-TAML... more
Degradation of two textile dyes, C.I.Acid Orange 7 (Orange II) and C.I. Reactive Red 2 (Procion Red MX-5B) bound to silica gel and cellulose by hydrogen peroxide catalyzed by Fe (III) complexed to Tetra-Amido Macrocyclic Ligands (Fe-TAML activators) at pH 10 was investigated. The performance of the oxidising system was characterized by conducting batch and column experiments. C.I.Acid Orange 7 and C.I. Reactive Red 2 on solid matrix after the addition of the Fe-TAML/H2O2 decolourize in initial time period of 10-20 minutes. The decolourisation rate of dyes on silica gel or on cellulose respectively was much slower than that in aqueous solution. On the silica gel. the degradation mechanism is the same as observed in aqueous solutions, first step is likely the formation of reactive species and the second step is the interaction of the reactive part with the desorbed dyes structure to release various species. The finding about decolourisation of the dyed cellulose leads to the conclusion that that Fe-TAML molecules must enter into the microfibril of cellulose and approach closely to the dye. Thus, the catalyst is not able to completely degrade the dye while bound to a fabric of structure such as cellulose
Research Interests:
“Molecular engineering” has been used to design and synthesize a successful catalyst for the 4-electron reduction of molecular oxygen to water. This catalyst operates at rates near those of the enzyme cytochrome-c oxidase and two orders... more
“Molecular engineering” has been used to design and synthesize a successful catalyst for the 4-electron reduction of molecular oxygen to water. This catalyst operates at rates near those of the enzyme cytochrome-c oxidase and two orders of magnitude greater than the best catalyst currently available, platinum. Knowledge of biochemical and inorganic reaction mechanisms suggested the catalyst design. This required construction of binary cyclophane porphyrins with a cofacial orientation which would permit the simultaneous interaction of two metal centers with one oxygen molecule. Early cofacial porphyrins were linked by functionalized aryl substituents on the meso position of the porphyrin ring and were ineffective as catalysts. More flexible and sophisticated syntheses led to two series of porphyrins with alkyl bridges attached at the meso and β positions of the porphyrin rings. In this way, the length of the bridges could be varied. The technique of rotating ring-disk voltammetry showed that the dicobalt β-linked dimer with 4-atom bridges, 17b, was an excellent catalyst for the 4-electron reduction, generating <4% hydrogen peroxide. HPLC analysis of the free-base precursor to 17b showed it was a mixture of three components, two of which were shown by mass spectroscopic analysis to bear monochloro substituents on one of the porphyrin rings. The chlorinated dimer was a better catalyst than the unfunctionalized parent, and this observation supports the concept that electronegative substituents may enhance the properties of these electrode catalysts. The heterobimetallic cobalt-aluminum and palladium-cobalt relatives of 17b behave catalytically as monomeric porphyrins. These and other observations have suggested a mechanism for this important multi-electron redox reaction which takes place in aqueous acid at a graphite electrode.
Abstract Os(n 2 -CS 2 )(CS)(CO)(PPh 3 ) 2 and [Os(n 2 -CS 2 Me)(CS)(CO)(PPh 3 ) 2 ]CF 3 SO 3 have been derived from Os(CS)(CO)(PPh 3 ) 3 and the dithioester-complex reacts with acids to give OsX 2 (CS) 2 (PPh 3 ) 2 or, after introduction... more
Abstract Os(n 2 -CS 2 )(CS)(CO)(PPh 3 ) 2 and [Os(n 2 -CS 2 Me)(CS)(CO)(PPh 3 ) 2 ]CF 3 SO 3 have been derived from Os(CS)(CO)(PPh 3 ) 3 and the dithioester-complex reacts with acids to give OsX 2 (CS) 2 (PPh 3 ) 2 or, after introduction of diethyldithiocarbamate, to give the dithiocarbonyl cation [Os(n 2 -S 2 CNEt 2 )(CS) 2 (PPh 3 ) 2 ] + : reaction of this last species with borohydride gives a thioformyl complex, Os(CHS)(n 2 -S 2 CNEt 2 )(CS)(PPh 3 ) 2 .
Abstract The thiocarboxamido-thiocarbonyl cation, [Os(n 2 -SCNMeptolyl)(CS)(CO)(PPh 3 ) 2 ] + , upon reaction with NaBH 4 , forms Os(CS 2 C NMeptolyl)H(CO)(PPh 3 ) 2 through an inter-ligand reaction; x-ray crystal structure analysis of... more
Abstract The thiocarboxamido-thiocarbonyl cation, [Os(n 2 -SCNMeptolyl)(CS)(CO)(PPh 3 ) 2 ] + , upon reaction with NaBH 4 , forms Os(CS 2 C NMeptolyl)H(CO)(PPh 3 ) 2 through an inter-ligand reaction; x-ray crystal structure analysis of Os(CS 2 C NMeptolyl)H(CO)(PPh 3 ) 2 confirms the presence of a four-membered metallocycle and further reaction with MeI produces what is formally a chelate di-carbene ligand in [ Os(C(SMe)SC NMeptolyl)H(CO)(PPh 3 ) 2 ] + .
J. Armstrong – Merck, UK A. Cannon – Beyond Benign Foundation, Wilmington, MA, USA T. Collins – Carnegie Mellon University, Pittsburgh, USA D. Constable – GlaxoSmithKline, King of Prussia, PA, USA B. Cue – Guiding Green, Ledyard, CT, USA... more
J. Armstrong – Merck, UK A. Cannon – Beyond Benign Foundation, Wilmington, MA, USA T. Collins – Carnegie Mellon University, Pittsburgh, USA D. Constable – GlaxoSmithKline, King of Prussia, PA, USA B. Cue – Guiding Green, Ledyard, CT, USA M. Hearn – Monash University, Melbourne, Australia J. Hutchinson – University of Oregon, USA J. Keriko – Jomo Kenyatta University of Agriculture and Technology, Nairobi, Kenya A. Morelli – Procter and Gamble, Egham, UK P. Moyna – Universidad de la República, Facultad de Quimica, Montevideo, Uruguay H. Nishide – Waseda University, Tokyo, Japan R. Noyori – RIKEN, Wako, Japan
Research Interests:
In the Institute for Green Oxidation Chemistry, we develop oxidation catalysts with useful lifetimes via an iterative design process in which oxidation-sensitive ligand groups are identified and replaced. The process has led to catalysts... more
In the Institute for Green Oxidation Chemistry, we develop oxidation catalysts with useful lifetimes via an iterative design process in which oxidation-sensitive ligand groups are identified and replaced. The process has led to catalysts with greatly enhanced stability toward oxidative and hydrolytic degradation. The iron catalysts described herein can be comprised exclusively of biochemically common elements. They are efficient and selective peroxide activators for many areas of technology. They are water-soluble and are effective in minute quantities (nanomolar to low micromolar) over a broad pH range. Various green chemistry applications are sketched.
The European Food Safety Authority (EFSA) has revised their estimate of the toxicity of bisphenol A (BPA) and, as a result, have recommended reducing the tolerable daily intake (TDI) by 20 000-fold. This would essentially ban the use of... more
The European Food Safety Authority (EFSA) has revised their estimate of the toxicity of bisphenol A (BPA) and, as a result, have recommended reducing the tolerable daily intake (TDI) by 20 000-fold. This would essentially ban the use of BPA in food packaging such as can liners, plastic food containers, and in consumer products. To come to this conclusion, EFSA used a systematic approach according to a pre-established protocol and included all guideline and nonguideline studies in their analysis. They found that Th-17 immune cells increased with very low exposure to BPA and used this endpoint to revise the TDI to be human health protective. A number of regulatory agencies including the European Medicines Agency (EMA) have written formal disagreements with several elements of EFSA's proposal. The European Commission will now decide whether to accept EFSA's recommendation over the objections of EMA. If the Commission accepts EFSA's recommendation, it will be a landmark acti...
High-Valent Transition Metal Chemistry. Miissbauer and EPR Studies of High-Spin (S = 2) Iron(1V) and ... Intermediate-Spin (S = 3/2) Iron(II1) Complexes with a ... Kimberly L. Kwtka,t Brian G. Forqt Michael P. HendricIQ Terrence J.... more
High-Valent Transition Metal Chemistry. Miissbauer and EPR Studies of High-Spin (S = 2) Iron(1V) and ... Intermediate-Spin (S = 3/2) Iron(II1) Complexes with a ... Kimberly L. Kwtka,t Brian G. Forqt Michael P. HendricIQ Terrence J. Collins,**t Clifton EF Rickard,l L. James ...
Nitrile solvents containing α-CH substituents are catalytically oxidized by the tetraamido-N-FeIII-aqua complex, 3, with t-butyl hydroperoxide. Every observable product resulting from 3 has been characterized. An FeIV–cyano complex, 5, is... more
Nitrile solvents containing α-CH substituents are catalytically oxidized by the tetraamido-N-FeIII-aqua complex, 3, with t-butyl hydroperoxide. Every observable product resulting from 3 has been characterized. An FeIV–cyano complex, 5, is the major inorganic product; the ...
... (f) Collins, T. J ... After stirring at 20 OC (30 min), air was admitted through a calcium chloride drying tube and an orange precipitate rapidly developed as the green precipitate disappeared (presumably as the result of oxidation of... more
... (f) Collins, T. J ... After stirring at 20 OC (30 min), air was admitted through a calcium chloride drying tube and an orange precipitate rapidly developed as the green precipitate disappeared (presumably as the result of oxidation of the iron(I1) complex by oxygen to iron(ll1)). ...
A multidisciplinary investigation of the technical and environmental performances of TAML/peroxide elimination of Bisphenol A compounds from water: destruction, oligomerisation, mechanisms, end product toxicity, and applications.
The present method provides a method of transferring oxygen to at least one oxidizable site on a target compound. The method includes the steps of selectively oxidizing an oxidizable site on a target compound by reacting in solution: the... more
The present method provides a method of transferring oxygen to at least one oxidizable site on a target compound. The method includes the steps of selectively oxidizing an oxidizable site on a target compound by reacting in solution: the target compound, a source of oxygen atoms, a source of a Lewis acid, such as a proton, alkali, alkaline earth, rare earth, transition metal or main group metal ion, and a catalyst. The catalyst has general structure (I) wherein Z is preferably N, but may include O and MO is a transition metal- oxo species. The Lewis acid binds to a bidentate secondary site on the Ch1substituent to form a Lewis acid-catalyst complex.

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