DOCSLIB.ORG

Unexpected Molecular Structure of a Putative Rhenium‐Dioxo

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Unexpected Molecular Structure of a Putative Rhenium‐Dioxo View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by eScholarship - University of California Lawrence Berkeley National Laboratory Recent Work Title Unexpected Molecular Structure of a Putative Rhenium-Dioxo-Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin-Type Ligand Environment. Permalink https://escholarship.org/uc/item/0jb3573k Journal ChemistryOpen, 8(10) ISSN 2191-1363 Authors Alemayehu, Abraham B Vazquez-Lima, Hugo Teat, Simon J et al. Publication Date 2019-10-18 DOI 10.1002/open.201900271 Peer reviewed eScholarship.org Powered by the California Digital Library University of California DOI: 10.1002/open.201900271 Communications 1 2 3 Unexpected Molecular Structure of a Putative Rhenium- 4 5 Dioxo-Benzocarbaporphyrin Complex. Implications for the 6 Highest Transition Metal Valence in a Porphyrin-Type 7 8 Ligand Environment 9 [a] [b] [c] [a] 10 Abraham B. Alemayehu, Hugo Vazquez-Lima, Simon J. Teat, and Abhik Ghosh* 11 12 period compounds CnF [5] and RgF [6] should also be moderately 13 A combination of quantum chemical calculations and synthetic 4 7 > stable. Porphyrins have long been known to stabilize high- 14 studies was used to address the possibility of very high ( 6) valent transition metal centers such as Fe(IV),[7] Mn(V), Cr(V), Ru 15 valence states of transition metals in porphyrin-type complexes. (VI), and Os(VI).[8] More recently, we have shown that corroles[9] 16 With corrole as a supporting ligand, DFT calculations ruled out can stabilize RuVIN[10] and OsVIN[11] centers as well as Mo(VI)[12] 17 Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted and W(VI),[13] the latter in the form of unique eight-coordinate 18 rhenium insertion into benzocarbaporphyrin (BCP) ligands on biscorrole complexes. Herein, we report our first results on 19 the other hand led to two products with different stoichiome- whether porphyrin-type ligands can stabilize a valence higher 20 tries – Re[BCP]O and Re[BCP]O2. To our surprise, single-crystal than six, focusing on rhenium. Rhenium is particularly promis- 21 structure determination of one of the complexes of the latter V ing because its heptavalent state is not only stable with oxide 22 type indicated an Re O center with a second oxygen bridging À (especially in the form of perrhenate, ReO À ), but also with a 23 the Re C bond. In other words, although the monooxo 4 variety of carbon ligands and even with hydride, the latter in 24 complexes Re[BCP]O are oxophilic, the BCP ligand cannot VII the form of the unique homoleptic ReH 2À anion.[14] 25 sustain a trans-Re (O)2 center. The search for metal valence 9 > We began our investigation by undertaking a ZORA scalar- 26 states 6 in porphyrin-type ligand environments must there- relativistic density functional theoretical (DFT) study (B3LYP-D3/ 27 fore continue. ZORA-STO-TZ2P; ADF)[23,24] of as yet experimentally unknown 28 ReVIIO and IrVIIO2 corrole derivatives (Scheme 1). In the Re 29 2 30 Chemists are perennially interested in exploring the limits of 31 chemical structure and bonding. In recent years, many 32 inorganic chemists, for example, have concerned themselves 33 with determining the highest possible valence or oxidation 34 states for different transition metals. Some notable experimen- 35 tally established examples of unusually high oxidation states 36 include Au(V), Hg(IV), and Ir(IX) in the form of AuF À ,[1] HgF ,[2] 37 6 4 and the IrO + cation,[3] respectively.[4] In our own laboratory, 38 4 Scheme 1. Molecular structures of putative Re(VII)- and Ir(VII)-dioxo com- quantum chemical studies have suggested that the seventh- 39 plexes. 40 41 [a] Dr. A. B. Alemayehu, Prof. Dr. A. Ghosh 42 Department of Chemistry case,[15] the lowest energy structures turned out to be (in order 43 UiT – The Arctic University of Norway 9037 Tromsø, Norway of increasing relative energy) an S=1 trans-ReVI(Cor*2À )(O) 44 2 E-mail: [email protected] species, an S=0 ReV(η2À O ) peroxo just 0.12 eV higher in 45 [b] Dr. H. Vazquez-Lima 2 energy, and finally the S=0 trans ReVII-dioxo complex 0.39 eV 46 Centro de Química, Instituto de Ciencias Universidad Autónoma de Puebla above the ground state. Experimentally as well, attempts to 47 Edif. IC9, CU, San Manuel oxygenate ReVO corroles did not yield any indication of an 48 72570 Puebla, Puebla, Mexico ReVIIO product. In the Ir case, we found two essentially 49 [c] Dr. S. J. Teat 2 Advanced Light Source equienergetic contenders for the ground state, namely an S= 1 50 Lawrence Berkeley National Laboratory trans-IrVI(Cor*2À )(O) species and the S=0 trans-IrVII(Cor3À )(O)2 51 Berkeley, CA 94720–8229, USA 2 species. The IrV(η2À O ) peroxo complex turned out to be some 52 Supporting information for this article is available on the WWW under 2 0.18 eV higher in energy than the lowest-energy Ir-dioxo 53 https://doi.org/10.1002/open.201900271 © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This species. Experimentally, however, the great majority of stable Ir- 54 is an open access article under the terms of the Creative Commons Attri- corroles are six-coordinate Ir(III) complexes[16] with strongly 55 bution Non-Commercial License, which permits use, distribution and re- bound axial amine or phosphine ligands and appear unsuitable 56 production in any medium, provided the original work is properly cited and is not used for commercial purposes. as precursors to high-valent Ir-oxo species. One-electron 57 ChemistryOpen 2019, 8, 1298–1302 1298 © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA Wiley VCH Dienstag, 22.10.2019 1910 / 149017 [S. 1298/1302] 1 Communications oxidation of these species also happens in a largely ligand- 1 centered manner, with only a small amount of Ir(IV) character in 2 the final product.[17] 3 In the wake of the unpromising exploratory DFT studies on 4 Re and Ir corroles, a significant breakthrough came from an 5 unexpected quarter. While searching for phosphorescent 5d 6 metalloporphyrinoids for use as oxygen sensors and as 7 sensitizers in photodynamic therapy,[18,19] attempted Re inser- 8 tion into two different meso-tetraarylbenzocarbaporphyrin 9 (BCP)[20,21] ligands with Re (CO) in refluxing 1,2,4-trichloroben- 10 2 10 zene led to not only Re[BCP]O but also a second product for 11 which high-resolution mass spectrometry indicated a molecular 12 formula “Re[BCP]O ” (BCP=TPBCP, TpFPBCP; Scheme 2); the 13 2 14 15 Figure 2. Comparison of the stacked 1H NMR spectra of “Re[TpFPBCP] 16 O2”(top), “Re[TPBCP]O2” (middle) and Au[TPBCP] (bottom) in CDCl3 at 298 K. 17 18 19 dioxygenated compounds relative to the monooxo complexes 20 (Figure 2). A comparison with the known, structurally charac- 21 terized, twofold-symmetric gold complex Au[TPBCP] proved 22 instructive.[20b] Although the meso-phenyl protons of the new Re 23 complexes could not be fully assigned because of mutual 24 Scheme 2. Meso-tetra(p-X-phenyl)-substituted benzocarbaporphyrin ligands used in this study. overlap, it was clear that they led to more numerous signals 25 relative to the Au complex. That is expected for the Re[BCP]O 26 complexes, because of the nonequivalence of the two macro- 27 cycle faces, but not for trans-Re[BCP]O , whose macrocycle faces 28 2 quotation marks indicate that the formula refers only to should be equivalent by symmetry. The 1H NMR data thus 29 stoichiometry but not to connectivity. The key question appeared to argue against a trans-Re-dioxo formulation. 30 accordingly was whether the latter contains an ReVII-dioxo Fortunately, single-crystal X-ray structures could be ob- 31 center. Both optical and 1H NMR spectra afforded intriguing tained for a pair of mono- and dioxygenated complexes, namely 32 clues as to the nature of these two complexes. Re[TpFPBCP]O and “Re[TpFPBCP]O ” (Table 1). The former 33 2 All four new Re-benzocarbaporphyrin complexes Re[BCP]O proved much as expected, with equatorial ReÀ C/N distances of 34 n (n=1, 2) were found to exhibit redshifted Soret-like features at 2.05–2.09 Å and an axial ReÀ O distance of 1.664(3) Å (Figure 3). 35 just under 500 nm. Interestingly, for both dioxygenated prod- 36 ucts, the intensity of this feature was found to be only about 37 half that of the monooxo complexes (Figure 1). 1H NMR spectra 38 also revealed a broader spread of the pyrrole β-protons for the 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Figure 3. Thermal ellipsoid plot for Re[TpFPBCP]O with probabilities at 50%. 55 Solvent molecules have been omitted for clarity. Selected bond distances Figure 1. UV/Vis spectra of Re[TPBCP]O, Re[TpFPBCP]O, “Re[TPBCP]O ” and (Å): Re1-N1 2.052(3); Re1-N2 2.082(3); Re1-N3 2.058(3); Re1-C21 2.085(4); Re1- 56 2 “Re[TpFPBCP]O2” in CH2Cl2. O1 1.664(3). 57 ChemistryOpen 2019, 8, 1298–1302 www.chemistryopen.org 1299 © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA Wiley VCH Dienstag, 22.10.2019 1910 / 149017 [S. 1299/1302] 1 Communications 1 Table 1. Selected crystal and refinement data. 2 Re[TpFPBCP]O “Re[TpFPBCP]O2” 3 Empirical formula C49H26F4N3ORe C50H28Cl2F4N3O2Re 4 Formula weight 934.93 1035.85 5 Temperature 100(2) K 100(2) K Wavelength 0.7288 Å 0.7288 Å 6 Crystal system Monoclinic Triclinic 7 Space group P21/c 8 Unit cell dimensions a =13.1484(9) Å α = 90° a=11.0937(4) Å α=87.5400(10)° b=12.8968(8) Å β = 102.763(3)° b=13.7012(5) Å β=68.1790(10)° 9 c=22.2407(15) Å γ = 90°.
Load more

Recommended publications
  • Osmium-Nitrido Corroles As NIR Indicators for Oxygen Sensors and Triplet Sensitizers for Organic Cite This: J
    Journal of Materials Chemistry C View Article Online PAPER View Journal | View Issue Osmium-nitrido corroles as NIR indicators for oxygen sensors and triplet sensitizers for organic Cite this: J. Mater. Chem. C, 2016, 4,5822 upconversion and singlet oxygen generation† Sergey M. Borisov,*a Abraham Alemayehub and Abhik Ghosh*b The photophysical properties of nitridoosmium(VI) corroles have been investigated. The complexes exhibit room temperature NIR phosphorescence (lmax 779–795 nm). Long decay times (110–150 msinsolution and 136–183 ms in polystyrene) are responsible for efficient quenching of the emission by oxygen. All the 1 Received 17th March 2016, complexes act as efficient sensitizers of singlet oxygen (quantum yields of O2 0.76–0.95). Optical oxygen Accepted 25th May 2016 sensors prepared on the basis of nitridoosmium(VI) corroles exhibit high photostability and excellent sensitivity DOI: 10.1039/c6tc01126h in the physiologically relevant range. The complexes have also been found to be promising sensitizers in triplet–triplet annihilation-based upconversion systems. Finally and not least, simple synthetic accessibility www.rsc.org/MaterialsC makes these dyes particularly attractive for application as optical materials. Creative Commons Attribution 3.0 Unported Licence. Introduction as triplet sensitizers in photon upconversion and as singlet oxygen generators in photodynamic therapy.31,32 Dyes exhibiting room temperature phosphorescence find numerous As porphyrin analogues with a rapidly unfolding chemistry, applications, for example,
    [Show full text]
  • Annual Report CTCC 2014
    The Centre for Theoretical CTCC and Computational Chemistry annual report 2014 The Centre for Theoretical CTCC and Computational Chemistry annual report 2014 Te Centre for Teoretical and The Centre for Theoretical Computational ChemistryCTCC CTCCand Computational Chemistry Table of ContentsannualT e reportCentre for Teoretical and2014 Computational Chemistry (CTCC) is a Norwegian Centre of Excel- A Year for Young Scientists ...................................................................................3 lence (CoE) established by the Research Council of Nor- From the Board of Directors ..............................................................................4 way (RCN) in July 2007. Te goal of the CoE program is to stimulate Norwegian research groups to establish 2014 in brief .......................................................................................................................................5 larger units focusing on frontier research at a high inter- Highlight: New insights on porphyrinoid comp ounds national level and to contribute to raising the quality of through studies of gauge-including magnetically Norwegian research. induced current densities .............................................................................................8 Te CTCC is one of 21 national CoEs in Norway and Highlight: Role of CRALBP for Dark-Adapted one of two centres in chemistry. It has two nodes of equal Selection of cis-Retinoids in the Eye .......................................................11 size, hosted by UiT
    [Show full text]
  • Sinchan Snigdha Adhikary
    Sinchan Snigdha Adhikary Curriculum Vitae Graduate Student, Dept. of ORFE Princeton University Contact Information Permanent Address : E-mail: [email protected] B.R.M.B. Road, Mother Teresa Sarani, Ismile, Asansol, PIN- 713301, Paschim Bardhaman, West Bengal, India. Personal Sex: Male Information Date of Birth: 22nd February, 1997 Place of Birth: Asansol, West Bengal, India Citizen: Indian Education I. (Pursuing) PhD program, ORFE, Princeton University (2020-present) II. Master of Statistics (M. Stat), Indian Statistical Institute, Kolkata (July 2018 - June 2020) 1. Total Percentage Score: 83.7% 2. Specialization: Advanced Probability III. Bachelor of Statistics (B. Stat)(Hons.), Indian Statistical Institute, Kolkata (July 2015 - June 2018). 1. Total Percentage Score: 78.61% 2. Major: Statistics IV. Higher Secondary Examination (Std 12), Asansol Old Station High School, (June 2013 - May 2015) 1. Total Percentage Score(Best 5 subjects including languages): 95.0% 2. Courses: Bengali, English, Mathematics, Physics, Chemistry, Biology V. Secondary Examination (Std 10), Asansol Ramakrishna Mission High School, (May 2003 - May 2013) 1. Total Percentage Score: 93.0% 2. Courses: Bengali, English, Mathematics, Physical Science, Life Science, History, Geography. Academic Achievements • Unofficial GRE Scores (Exam date 1st July, 2019): Quantitative 169/170, Verbal 157/170, and Honors Analytical Writing 3.5/6 . • Unofficial TOEFL Scores (Exam date 4th October, 2019): Reading 29/30, Listening 25/30, Speaking 22/30, Writing 27/30. • Unofficial Mathematics Subject GRE Scores (Exam date 26th October, 2019): 970 out of 990, percentile 99% . 1 • Secured All India rank 1 in National Eligibility Test (Mathematical Sciences), held by CSIR-HRDG India-wide at 16th June, 2019.
    [Show full text]
  • American Scientist the Magazine of Sigma Xi, the Scientific Research Society
    A reprint from American Scientist the magazine of Sigma Xi, The Scientific Research Society This reprint is provided for personal and noncommercial use. For any other use, please send a request to Permissions, American Scientist, P.O. Box 13975, Research Triangle Park, NC, 27709, U.S.A., or by electronic mail to [email protected]. ©Sigma Xi, The Scientific Research Society and other rightsholders Perspective The Grammar of the Elements Did the Sanskrit alphabet influence Mendeleev’s periodic table? Abhik Ghosh and Paul Kiparsky mitri Ivanovich Mendeleev might have led Mendeleev to reference was not the first to recog- Sanskrit in this way. nize the periodicity of the In general terms, the origin of Men- chemical elements or even deleev’s periodic table is fairly well- Dto construct a primitive periodic table. known. As a freshly tenured profes- He did go much further than his peers, sor at Saint Petersburg University in however, in conceptualizing periodic- Russia in 1867, Mendeleev found him- ity as a fundamental law governing self responsible for teaching in organic the nature of the elements. Based on chemistry with no suitable textbook at that insight, whenever the properties hand. Characteristically, he set about of a given element didn’t fit the over- writing his own—Osnovy Khimii [Prin- all pattern, he famously left an empty ciples of Chemistry]—between 1868 spot in his table for an as yet undiscov- and 1870. During this period, while ered element. He used the prefixes eka, searching for a sensible order for dis- dvi, and tri, Sanskrit for the numbers cussing the chemistry of the approxi- es such as Sanskrit, and there is strong one, two, and three, to name these hypo- mately 65 elements known at the time, evidence that Mendeleev cultivated thetical elements, referring to the num- he hit upon the idea of the “periodic friends in that milieu.
    [Show full text]
  • Curriculum Vitae
    Sayar Karmakar University of Florida Department of Statistics Phone: (312) 709-0684 230 Newell Drive Email: [email protected] Gainesville, FL 32601 Tel: (352) 392-1941 Employment (Aug 2018-Current) Assistant Professor of Statistics, University of Florida Education Ph.D., Statistics, University of Chicago, June 2018 Master of Statistics, Indian Statistical Institute, 2013. Bachelor of Statistics , Indian Statistical Institute, 2011. Research Grants Awarded NSF DMS ATD program 2124222 New algorithms for inference and predictions on large geospatial datasets. 2021-24. Role- Solo P.I. $200,000. Link: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2124222&HistoricalAwards=false Start-up grant from University of Florida. Project name: High dimensional inference for dependent data. Role- Solo P.I. $83,924 AMS Simons Travel Grant for 2021-2024. $5000 Research Publications Updates: https://sayarkarmakar.github.io. Published Journal Articles 1. Simultaneous inference for time-varying models: Sayar Karmakar, Stefan Richter, Wei Biao Wu; To appear at Journal of Econometrics. Link: https://doi.org/10.1016/j.jeconom.2021.03.002 2. Optimal Gaussian approximation for multiple time-series: Sayar Karmakar, Wei Biao Wu; Statistica Sinica 30, 1399-1417 (2020) Presented in Statistica Sinica Invited Papers Session JSM 2020. Link: https://doi.org/10.5705/ss.202017.0303 Arxiv version: https://arxiv.org/abs/2001.10164 3. Shrinkage estimation with singular priors and an application to small area estimation. Ryumei Nakada (Graduate student), Tatsuya Kubokawa, Malay Ghosh and Sayar Karmakar. Journal of Multivariate Analysis Volume 183, May 2021 Link: https://doi.org/10.1016/j.jmva.2021.104726 Sayar Karmakar 2 4. Long term prediction intervals of economic time-series: Marek Chudy∗, Sayar Karmakar∗, Wei Biao Wu; Empirical Economics 58, 191-222 (2020) [* Alphabetical order] Link: https://doi.org/10.1007/s00181-019-01689-2 5.
    [Show full text]
  • Final Program of ICPP-5
    Program International Conference on Porphyrins and Phthalocyanines 1 MONDAY Program of ICPP-5 Copyright © 2008 Society of Porphyrins & Phthalocyanines Moscow Russia - July 6-11, 2008 http://www.icpp-spp.org MONDAY 2 International Conference on Porphyrins and Phthalocyanines Program Monday 7 July, 2008 - AM Award Lecture Large Hall Chaired by: Daniel G. Nocera 10:00 to 11:00 H. B. Gray Heme Protein Folding Landscapes Symposia Lectures Synthesis of Porphyrins and Phthalocyanines Large Hall Chaired by: Michael J. Cook and Andrey Mironov 11:30 to 12:00 Harry Anderson Synthesis of porphyrin dimers for two-photon excited photodynamic therapy 12:00 to 12:20 Yulia Gorbunova, Kirill Birin, Alexander Martynov, Aslan Tsivadze Synthetic approaches to heteroleptic sandwich tetrapyrroles 12:20 to 12:40 José Cavaleiro Synthesis of New Glycoporphyrin Derivatives 12:40 to 13:00 Ozer Bekaroglu Ball-type or cofacial bis-phthalocyanines: synthesis and properties 13:00 to 13:20 Hidemitsu Uno Bicyclo[[2.2.2]octadiene-fused Porphyrins. Structures, Properties, and Reactivities 13:20 to 13:40 Penelope Brothers, Amelia Albrett, Peter Boyd, Jeanet Conradie, Abhik Ghosh Corroles containing coordinated boron Moscow Russia - July 6-11, 2008 Copyright © 2008 Society of Porphyrins & Phthalocyanines http://www.icpp-spp.org Program International Conference on Porphyrins and Phthalocyanines 3 MONDAY Tumor Imaging, Photodynamic Therapy and other Medical Applications of Porphyrin-Based Compounds Beige Hall Chaired by: Ravindra Pandey and Jianjun Guo 11:30 to 12:00 Charles
    [Show full text]
  • Print This Article
    Bengal Journal of Otolaryngology and Head Neck Surgery Official Publication of The Association of Otolaryngologists of India, West Bengal Volume 23 No. 3 - December, 2015 EDITORIAL BOARD CONTENTS From the desk of the Editor Editor Main Article Dr Saumendra Nath Bandyopadhyay Hyperbaric Oxygen Therapy in the treatment of Idiopathic 87 Sudden Sensorineural Hearing Loss Editorial Secretary Debasish Guha, Shaoni Sanyal, Chayan Bhattacharyya, Abhijit Santra, Dr Swagatam Banerjee Swagatam Banerjee Three Years’ Experience of Management of Different Types 92 Members of Rhinosporidiosis in Rural Part of Western West Bengal Dr Sarmishtha Bandyopadhyay Debdulal Chakraborty, Chiranjib Das, Rajesh Hansda Dr Radheshyam Mahato Identifying Recurrent Laryngeal Nerve in Thyroid Surgery 99 Using Relationship with Superior Parathyroid Gland and Treasurer Tubercle of Zuckerkandl Dr Snehasis Barman Somesh Mozumder, Shirish Dubey, Aniruddha Dam, Anup Kumar Bhowmick Ex-Officio Members Acetic Acid Instillation after Canal Wall Down 104 Dr Prabir Basu Mastoidectomy Hamsa Shetty, Gangadhara K S (President) Dr Dwaipayan Mukherjee (Hony. Secretary) Invited Article Operating Room Essentials for Budding Doctors - A 109 This journal is indexed Perspective in OCLC WorldCat, Tushar Chakravorty Google Scholar, WHO Hinari, OAIster, BASE, Case Series abcGATE, CiteFactor, SIS, Ossicular Status in Cholesteatoma : Experience in a State 116 JournalTOCS, OAJI, EZB Medical College of West Bengal and listed in AcademicKeys Somesh Mozumder, Arunabha Sengupta, Alok Ranjan Mondal,
    [Show full text]
  • Stable Platinum(IV) Corroles: Synthesis, Molecular Structure, and Room-Temperature Near-IR Phosphorescence
    Lawrence Berkeley National Laboratory Recent Work Title Stable Platinum(IV) Corroles: Synthesis, Molecular Structure, and Room-Temperature Near-IR Phosphorescence. Permalink https://escholarship.org/uc/item/9n05q3k2 Journal ACS omega, 3(8) ISSN 2470-1343 Authors Alemayehu, Abraham B McCormick, Laura J Gagnon, Kevin J et al. Publication Date 2018-08-17 DOI 10.1021/acsomega.8b01149 Peer reviewed eScholarship.org Powered by the California Digital Library University of California This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Article Cite This: ACS Omega 2018, 3, 9360−9368 http://pubs.acs.org/journal/acsodf Stable Platinum(IV) Corroles: Synthesis, Molecular Structure, and Room-Temperature Near-IR Phosphorescence † ‡ ‡ § Abraham B. Alemayehu, Laura J. McCormick, Kevin J. Gagnon, Sergey M. Borisov, † and Abhik Ghosh*, † Department of Chemistry, UiTThe Arctic University of Norway, N-9037 Tromsø, Norway ‡ Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720-8229, United States § Institute of Analytical Chemistry and Food Chemistry, NAWI Graz, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria *S Supporting Information ABSTRACT: A series of stable Pt(IV) corrole complexes with the general IV 3− formula Pt [TpXPC](m/p-C6H4CN)(py), where TpXPC is the trianion of a tris(p-X-phenyl)corrole and X = CF3, H, and CH3, has been synthesized, affording key physicochemical data on a rare and elusive class of metallocorroles. Single-crystal X-ray structures of two of the complexes revealed very short equatorial Pt−N distances of 1.94−1.97 Å, an axial Pt−C distance of ∼2.03 Å, and an axial Pt−N distance of ∼2.22 Å.
    [Show full text]
  • A Combined Experimental and DFT Study of Metal–Ligand Interactions
    RSC Advances View Article Online PAPER View Journal | View Issue Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand Cite this: RSC Adv., 2020, 10,533 interactions† Kolle E. Thomas,a Nicolas Desbois,b Jeanet Conradie, ac Simon J. Teat, d Claude P. Gros *b and Abhik Ghosh *a Given that noninnocent and metalloradical-type electronic structures are ubiquitous among dipyrrin- bisphenolate (DPP) complexes, we synthesized the gold(III) derivatives as potentially innocent paradigms against which the properties of other metallo-DPP derivatives can be evaluated. Electronic absorption Received 7th November 2019 spectra, electrochemical studies, a single-crystal X-ray structure, and DFT calculations all suggest that Accepted 18th December 2019 the ground states of the new complexes indeed correspond to an innocent AuIII–DPP3À, paralleling DOI: 10.1039/c9ra09228e a similar description noted for Au corroles. Interestingly, while DFT calculations indicate purely ligand- rsc.li/rsc-advances centered oxidations, reduction of AuDPP is predicted to occur across both the metal and the ligand. Creative Commons Attribution-NonCommercial 3.0 Unported Licence. 1. Introduction 2. Results and discussion 2.1 Physical measurements The dipyrrin-bisphenols (H3DPP) are an emerging class of ligands that share a number of similarities with corroles Three Au(III) meso-para-X-phenyl dipyrrin-bisphenolate 1 ¼ (Fig. 1). Thus, they are triprotic, afford a square-planar envi- complexes Au[XDPP] with X CF3, H, and Me were obtained ronment for coordinated metals, and even exhibit redox-active as blue solids in 50–77% yields via the interaction of the cor- behavior remarkably similar to that of corroles.2,3 Thus, like responding free ligands and a threefold molar excess of Au(III) – 12 This article is licensed under a their corrole analogues,4 6 a number of M[DPP] derivatives (M ¼ acetate in pyridine.
    [Show full text]
  • Infrared Spectroelectrochemistry of Iron-Nitrosyl Triarylcorroles
    Marquette University e-Publications@Marquette Chemistry Faculty Research and Publications Chemistry, Department of 3-2020 Infrared Spectroelectrochemistry of Iron-Nitrosyl Triarylcorroles. Implications for Ligand Noninnocence Md. Hafizur Rahman Michael D. Ryan Hugo Vazquez-Lima Abraham Alemayehu Abhik Ghosh Follow this and additional works at: https://epublications.marquette.edu/chem_fac Part of the Chemistry Commons Marquette University e-Publications@Marquette Chemistry Faculty Research and Publications/College of Arts and Sciences This paper is NOT THE PUBLISHED VERSION. Access the published version via the link in the citation below. Inorganic Chemistry, Vol. 59, No. 5 (March 2020): 3232-3238. DOI. This article is © American Chemical Society and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society. Infrared Spectroelectrochemistry of Iron- Nitrosyl Triarylcorroles. Implications for Ligand Noninnocence Md. Hafizur Rahman Department of Chemistry, Marquette University, 1414 West Clybourn Street, Milwaukee, Wisconsin Michael D. Ryan Department of Chemistry, Marquette University, 1414 West Clybourn Street, Milwaukee, Wisconsin Hugo Vazquez-Lima Department of Chemistry, UiT—The Arctic University of Tromsø, 9037 Tromsø, Norway Centro de Química, Instituto de Ciencias, Universidad Autónoma de Puebla, Edif. IC9, CU, San Manuel, 72570 Puebla, Puebla, Mexico Abraham Alemayehu Department of Chemistry, UiT—The Arctic University of Tromsø, 9037 Tromsø, Norway Abhik Ghosh Department of Chemistry, UiT—The Arctic University of Tromsø, 9037 Tromsø, Norway Abstract Recent DFT calculations have suggested that iron nitrosyl triarylcorrole complexes have substantial {FeNO}7–corrole•2– character.
    [Show full text]
  • 43Rd Rocky Mountain Conference on Analytical Chemistry
    Rocky Mountain Conference on Magnetic Resonance Volume 43 43rd Rocky Mountain Conference on Article 1 Analytical Chemistry July 2001 43rd Rocky Mountain Conference on Analytical Chemistry Follow this and additional works at: https://digitalcommons.du.edu/rockychem Part of the Chemistry Commons, Materials Science and Engineering Commons, and the Physics Commons Recommended Citation (2001) "43rd Rocky Mountain Conference on Analytical Chemistry," Rocky Mountain Conference on Magnetic Resonance: Vol. 43 , Article 1. Available at: https://digitalcommons.du.edu/rockychem/vol43/iss1/1 This work is licensed under a Creative Commons Attribution 4.0 License. This Article is brought to you for free and open access by Digital Commons @ DU. It has been accepted for inclusion in Rocky Mountain Conference on Magnetic Resonance by an authorized editor of Digital Commons @ DU. For more information, please contact [email protected],dig- [email protected]. et al.: 43rd RMCAC Final Program and Abstracts 43RD ROCKY MOUNTAIN CONFERENCE ON ANALYTICAL CHEMISTRY July 29–August 2, 2001 Denver Marriott City Center • Denver, Colorado Table of Contents ORGANIZERS AND CHAIRPERSONS . .2 ROCKY MOUNTAIN CONFERENCE INFORMATION . .3 REGISTRATION SCHEDULE OF SOCIAL EVENTS SHUTTLE SERVICE TO AND FROM DIA MESSAGES HOTEL ACCOMMODATIONS AIRFARE ROCKY MOUNTAIN CONFERENCE-AT-A-GLANCE . .4 EXHIBITORS & SPONSORS FOR THE 43RD ROCKY MOUNTAIN CONFERENCE . .5 MARIE CURRIE PRESENTATION . .6 SYMPOSIA SCHEDULE: ELECTROCHEMISTRY . .7 ENVIRONMENTAL CHEMISTRY . .8 EPR SESSIONS . .9–15 EPR POSTER SESSIONS . .11–15 GENERAL POSTER SESSIONS . .16 ICP-MS . .17 LASERS & MATERIALS CHEMISTRY . .18 LUMINESCENCE . .19–20 NMR ORAL SESSIONS . .21–23 NMR POSTER SESSIONS . .24–27 MS, GC/MS, LC/MS .
    [Show full text]
  • Acs.Inorgchem.0C00654.Pdf
    Electrophilic Activation of Osmium-Nitrido Corroles The OsN Triple Bond as a -Acceptor Metallaligand in a Heterobimetallic OsVIN-PtII Complex Reinholdt, Anders; Alemayehu, Abraham B.; Gagnon, Kevin J.; Bendix, Jesper; Ghosh, Abhik Published in: Inorganic Chemistry DOI: 10.1021/acs.inorgchem.0c00654 Publication date: 2020 Document version Publisher's PDF, also known as Version of record Document license: CC BY Citation for published version (APA): Reinholdt, A., Alemayehu, A. B., Gagnon, K. J., Bendix, J., & Ghosh, A. (2020). Electrophilic ActivationVI of II Osmium-Nitrido Corroles: The OsN Triple Bond as a -Acceptor Metallaligand in a Heterobimetallic Os N-Pt Complex. Inorganic Chemistry, 59, 5276-5280. https://doi.org/10.1021/acs.inorgchem.0c00654 Download date: 02. okt.. 2021 This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. pubs.acs.org/IC Communication Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π‑Acceptor Metallaligand in a Heterobimetallic OsVIN−PtII Complex Anders Reinholdt, Abraham B. Alemayehu, Kevin J. Gagnon, Jesper Bendix,* and Abhik Ghosh* Cite This: Inorg. Chem. 2020, 59, 5276−5280 Read Online ACCESS Metrics & More Article Recommendations *sı Supporting Information ABSTRACT: Presented herein is a first investigation of the chemical reactivity of osmium-nitrido corroles, which are known for their unusual thermal, chemical, and photochemical stability. Elemental chlorine perchlorinates the β-positions of the triarylcorrole but leaves the OsN unit untouched. The OsN unit is also unaffected by a variety of other electrophilic and nucleophilic reagents.
    [Show full text]