Lawrence Que, Jr.
University of Minnesota-Twin Cities
H-index: 130
North America-United States
Description
Lawrence Que, Jr., With an exceptional h-index of 130 and a recent h-index of 51 (since 2020), a distinguished researcher at University of Minnesota-Twin Cities,
His recent articles reflect a diverse array of research interests and contributions to the field:
Formation of a Reactive [Mn (III)− O− Ce (IV)] Species and its Facile Equilibrium with Related Mn (IV)(OX)(X= Sc or H) Complexes
A tale of two topological isomers: Uptuning [FeIV(O)(Me4cyclam)]2+ for olefin epoxidation
NMR and Mössbauer Studies Reveal a Temperature-Dependent Switch from S = 1 to 2 in a Nonheme Oxoiron(IV) Complex with Faster C–H Bond Cleavage Rates
Class Ib Ribonucleotide Reductases: Activation of a Peroxido-MnIIMnIII to Generate a Reactive Oxo-MnIIIMnIV Oxidant
106-fold faster C–H bond hydroxylation by a CoIII,IV2(µ-O)2 complex [via a CoIII2(µ-O)(µ-OH) intermediate] versus its FeIIIFeIV analog
Small molecule activation and synthetic analogues: general discussion
Electron transfer, spectroscopy and theory: general discussion
Explorations of the nonheme high-valent iron-oxo landscape: crystal structure of a synthetic complex with an [Fe IV2 (μ-O) 2] diamond core relevant to the chemistry of sMMOH
Professor Information
University | University of Minnesota-Twin Cities |
---|---|
Position | Chemistry Department |
Citations(all) | 62281 |
Citations(since 2020) | 12080 |
Cited By | 55828 |
hIndex(all) | 130 |
hIndex(since 2020) | 51 |
i10Index(all) | 532 |
i10Index(since 2020) | 271 |
University Profile Page | University of Minnesota-Twin Cities |
Top articles of Lawrence Que, Jr.
Formation of a Reactive [Mn (III)− O− Ce (IV)] Species and its Facile Equilibrium with Related Mn (IV)(OX)(X= Sc or H) Complexes
Lewis acid‐bound high valent Mn‐oxo species are of great importance due to their relevance to photosystem II. Here, we report the synthesis of a unique [(BnTPEN)Mn(III)−O−Ce(IV)(NO3)4]+ adduct (2) by the reaction of (BnTPEN)Mn(II) (1) with 4 eq. ceric ammonium nitrate. 2 has been characterized using UV/Vis, NMR, resonance Raman spectroscopy, as well as by mass spectrometry. Treatment of 2 with Sc(III)(OTf)3 results in the formation of (BnTPEN)Mn(IV)−O−Sc(III) (3), while HClO4 addition to 2 forms (BnTPEN)Mn(IV)−OH (4), reverting to 2 upon Ce(III)(NO3)3 addition. 2 can also be prepared by the oxidation of 1 eq. Ce(III)(NO3)3 with [(BnTPEN)Mn(IV)=O]2+ (5). In addition, the EPR spectroscopy revealed the elegant temperature‐dependent equilibria between 2 and Mn(IV) species. The binding of redox‐active Ce(IV) boosts electron transfer efficiency of 2 towards ferrocenes. Remarkably, the newly …
Authors
Sikha Gupta,Pragya Arora,Rakesh Kumar,Ayushi Awasthi,Bittu Chandra,Raju Eerlapally,Jin Xiong,Yisong Guo,Lawrence Que Jr,Apparao Draksharapu
Journal
Angewandte Chemie
Published Date
2024/1/15
A tale of two topological isomers: Uptuning [FeIV(O)(Me4cyclam)]2+ for olefin epoxidation
TMC-anti and TMC-syn, the two topological isomers of [FeIV(O)(TMC)(CH3CN)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, or Me4cyclam), differ in the orientations of their FeIV=O units relative to the four methyl groups of the TMC ligand framework. The FeIV=O unit of TMC-anti points away from the four methyl groups, while that of TMC-syn is surrounded by the methyl groups, resulting in differences in their oxidative reactivities. TMC-syn reacts with HAT (hydrogen atom transfer) substrates at 1.3- to 3-fold faster rates than TMC-anti, but the reactivity difference increases dramatically in oxygen-atom transfer reactions. R2S substrates are oxidized into R2S=O products at rates 2-to-3 orders of magnitude faster by TMC-syn than TMC-anti. Even more remarkably, TMC-syn epoxidizes all the olefin substrates in this study, while TMC-anti reacts only with cis-cyclooctene but at a 100-fold slower rate …
Authors
Bittu Chandra,Faiza Ahsan,Yuan Sheng,Marcel Swart,Lawrence Que Jr
Journal
Proceedings of the National Academy of Sciences
Published Date
2024/3/19
NMR and Mössbauer Studies Reveal a Temperature-Dependent Switch from S = 1 to 2 in a Nonheme Oxoiron(IV) Complex with Faster C–H Bond Cleavage Rates
S = 2 FeIV═O centers generated in the active sites of nonheme iron oxygenases cleave substrate C–H bonds at rates significantly faster than most known synthetic FeIV═O complexes. Unlike the majority of the latter, which are S = 1 complexes, [FeIV(O)(tris(2-quinolylmethyl)amine)(MeCN)]2+ (3) is a rare example of a synthetic S = 2 FeIV═O complex that cleaves C–H bonds 1000-fold faster than the related [FeIV(O)(tris(pyridyl-2-methyl)amine)(MeCN)]2+ complex (0). To rationalize this significant difference, a systematic comparison of properties has been carried out on 0 and 3 as well as related complexes 1 and 2 with mixed pyridine (Py)/quinoline (Q) ligation. Interestingly, 2 with a 2-Q-1-Py donor combination cleaves C–H bonds at 233 K with rates approaching those of 3, even though Mössbauer analysis reveals 2 to be S = 1 at 4 K. At 233 K however, 2 becomes S = 2, as shown by its 1H NMR spectrum …
Authors
Waqas Rasheed,Nabhendu Pal,Ahmed M Aboelenen,Saikat Banerjee,Williamson N Oloo,Johannes EMN Klein,Ruixi Fan,Jin Xiong,Yisong Guo,Lawrence Que Jr
Journal
Journal of the American Chemical Society
Published Date
2024/2/1
Class Ib Ribonucleotide Reductases: Activation of a Peroxido-MnIIMnIII to Generate a Reactive Oxo-MnIIIMnIV Oxidant
In the postulated catalytic cycle of class Ib Mn2 ribonucleotide reductases (RNRs), a MnII2 core is suggested to react with superoxide (O2·–) to generate peroxido-MnIIMnIII and oxo-MnIIIMnIV entities prior to proton-coupled electron transfer (PCET) oxidation of tyrosine. There is limited experimental support for this mechanism. We demonstrate that [MnII2(BPMP)(OAc)2](ClO4) (1, HBPMP = 2,6-bis[(bis(2 pyridylmethyl)amino)methyl]-4-methylphenol) was converted to peroxido-MnIIMnIII (2) in the presence of superoxide anion that converted to (μ-O)(μ-OH)MnIIIMnIV (3) via the addition of an H+-donor (p-TsOH) or (μ-O)2MnIIIMnIV (4) upon warming to room temperature. The physical properties of 3 and 4 were probed using UV–vis, EPR, X-ray absorption, and IR spectroscopies and mass spectrometry. Compounds 3 and 4 were capable of phenol oxidation to yield a phenoxyl radical via a concerted PCET oxidation …
Authors
Lorna Doyle,Adriana Magherusan,Shuangning Xu,Kayleigh Murphy,Erik R Farquhar,Florian Molton,Carole Duboc,Lawrence Que Jr,Aidan R McDonald
Journal
Inorganic Chemistry
Published Date
2024/1/17
106-fold faster C–H bond hydroxylation by a CoIII,IV2(µ-O)2 complex [via a CoIII2(µ-O)(µ-OH) intermediate] versus its FeIIIFeIV analog
The hydroxylation of C–H bonds can be carried out by the high-valent CoIII,IV2(µ-O)2 complex 2a supported by the tetradentate tris(2-pyridylmethyl)amine ligand via a CoIII2(µ-O)(µ-OH) intermediate (3a). Complex 3a can be independently generated either by H-atom transfer (HAT) in the reaction of 2a with phenols as the H-atom donor or protonation of its conjugate base, the CoIII2(µ-O)2 complex 1a. Resonance Raman spectra of these three complexes reveal oxygen-isotope-sensitive vibrations at 560 to 590 cm−1 associated with the symmetric Co–O–Co stretching mode of the Co2O2 diamond core. Together with a Co•••Co distance of 2.78(2) Å previously identified for 1a and 2a by Extended X-ray Absorption Fine Structure (EXAFS) analysis, these results provide solid evidence for their “diamond core” structural assignments. The independent generation of 3a allows us to investigate HAT reactions of 2a with …
Authors
Yan Li,Chase Abelson,Lawrence Que Jr,Dong Wang
Journal
Proceedings of the National Academy of Sciences
Published Date
2023/12/19
Small molecule activation and synthetic analogues: general discussion
Leigh Aldous opened the discussion of the paper by Carole Duboc: Since the CoFe has a lower overpotential for H2 production, the current will be much lower than those of NiFe and FeFe (even if they have the same kinetic parameters). So, was there any evidence for electrocatalytic ability, eg even at slow scan rates? This Co–Fe complex was in theory very promising compared to Ni–Fe and Fe–Fe because of the more positive reduction potential, but in my mind it needs to have much better parameters to have any current due to the lower overpotential. So, have you tried hour-long reduction reactions, eg by reducing with cobaltocene? Does it have any activity at all, or is no H2 ever produced?Carole Duboc answered: The CoFe complex can be reduced by one electron and its reduced form has been characterized. We have experiments showing that it cannot directly react with H+ and needs to be further reduced …
Authors
Leigh Aldous,Peter Comba,Serena DeBeer,Abhishek Dey,Apparao Draksharapu,Carole Duboc,Shinobu Itoh,Kenneth Karlin,Subrata Kundu,Rocío López Domene,Jean-Didier Maréchal,Shyamalava Mazumdar,Rabindranath Mukherjee,David Parker,Anca Pordea,Lawrence Que,Sankar Prasad Rath,Peter Sadler,Chivukula Sastri,Siegfried Schindler,Volker Schünemann,Sayam Sen Gupta,Edward I Solomon,T Daniel P Stack
Journal
Faraday Discussions
Published Date
2022
Electron transfer, spectroscopy and theory: general discussion
Shyamalava Mazumdar opened the discussion of the paper by Abhishek Dey: Thank you for the excellent talk. You talked about the possibilities of different mechanisms in model systems. What is the mechanism in the case of real proteins, such as peroxidase or oxygenases? How does the asymmetric protein environment with very well de ned channels etc. affect the pathways?Abhishek Dey answered: The whole point of including the second sphere residues is not only to mimic the function of the enzymes but also to mimic the mechanism of the enzyme. We have reported iron porphyrins with pendant pyridine and amine groups which form compound I from peroxides at rates faster than that of HRPs (see ref. 1). Accordingly, these were found to be functional models of HRP and in some cases show a ping-pong mechanism with comparable Km and Kcal (see ref. 2). Apart from the second sphere residues …
Authors
Anjali Anilkumar,Philip Ash,Akhil R Chakravarty,Peter Comba,Serena DeBeer,Abhishek Dey,Apparao Draksharapu,Debabrata Goswami,Shinobu Itoh,Kenneth Karlin,KV Lakshmi,Shyamalava Mazumdar,Dimitrios Pantazis,David Parker,Lawrence Que,Gopalan Rajaraman,Sankar Prasad Rath,Chivukula Sastri,Sayam Sen Gupta,Edward I Solomon
Journal
Faraday Discussions
Published Date
2022
Explorations of the nonheme high-valent iron-oxo landscape: crystal structure of a synthetic complex with an [Fe IV2 (μ-O) 2] diamond core relevant to the chemistry of sMMOH
Methanotrophic bacteria utilize methane monooxygenase (MMO) to carry out the first step in metabolizing methane. The soluble enzymes employ a hydroxylase component (sMMOH) with a nonheme diiron active site that activates O2 and generates a powerful oxidant capable of converting methane to methanol. It is proposed that the diiron(II) center in the reduced enzyme reacts with O2 to generate a diferric-peroxo intermediate called P that then undergoes O–O cleavage to convert into a diiron(IV) derivative called Q, which carries out methane hydroxylation. Most (but not all) of the spectroscopic data of Q accumulated by various groups to date favor the presence of an FeIV2(μ-O)2 unit with a diamond core. The Que lab has had a long-term interest in making synthetic analogs of iron enzyme intermediates. To this end, the first crystal structure of a complex with a FeIIIFeIV(μ-O)2 diamond core was reported in 1999 …
Authors
Gregory T Rohde,Genqiang Xue,Lawrence Que
Journal
Faraday discussions
Published Date
2022
Professor FAQs
What is Lawrence Que, Jr.'s h-index at University of Minnesota-Twin Cities?
The h-index of Lawrence Que, Jr. has been 51 since 2020 and 130 in total.
What are Lawrence Que, Jr.'s top articles?
The articles with the titles of
Formation of a Reactive [Mn (III)− O− Ce (IV)] Species and its Facile Equilibrium with Related Mn (IV)(OX)(X= Sc or H) Complexes
A tale of two topological isomers: Uptuning [FeIV(O)(Me4cyclam)]2+ for olefin epoxidation
NMR and Mössbauer Studies Reveal a Temperature-Dependent Switch from S = 1 to 2 in a Nonheme Oxoiron(IV) Complex with Faster C–H Bond Cleavage Rates
Class Ib Ribonucleotide Reductases: Activation of a Peroxido-MnIIMnIII to Generate a Reactive Oxo-MnIIIMnIV Oxidant
106-fold faster C–H bond hydroxylation by a CoIII,IV2(µ-O)2 complex [via a CoIII2(µ-O)(µ-OH) intermediate] versus its FeIIIFeIV analog
Small molecule activation and synthetic analogues: general discussion
Electron transfer, spectroscopy and theory: general discussion
Explorations of the nonheme high-valent iron-oxo landscape: crystal structure of a synthetic complex with an [Fe IV2 (μ-O) 2] diamond core relevant to the chemistry of sMMOH
...
are the top articles of Lawrence Que, Jr. at University of Minnesota-Twin Cities.
What is Lawrence Que, Jr.'s total number of citations?
Lawrence Que, Jr. has 62,281 citations in total.