Dr Peter Portius

Department of Chemistry

Senior Lecturer in Inorganic Chemistry and Level 3 Coordinator

Level 3 Coordinator

p.portius@sheffield.ac.uk
+44 114 222 9385

Dainton Building

Full contact details

Dr Peter Portius
Department of Chemistry
Dainton Building
13 Brook Hill
Sheffield
S3 7HF

Profile

Dr. Portius obtained a PhD in Chemistry from Humboldt University in Berlin in 2001, where he worked under the supervision of Prof. AC Filippou on the reactivity of germanium(II) compounds. After his PhD he became a postdoctoral researcher at the University of Nottingham, where he also was a Humboldt Fellow and a Marie Curie Fellow.

In 2005 he became a postdoctoral researcher and then research associate at the University of Bonn. In 2007 he was appointed as an EPSRC Advanced Research Fellow at the University of Sheffield, where he was appointed lecturer in 2010.

Qualifications

MRSC
FHEA
Member of GDCh

Research interests

Our scientific interests are in the field of high energy compounds from preparation to understanding and controlling reactivity as well as in the area of practical applications. We want to understand the factors which govern their stability (with respect to thermal and mechanical shocks as well as to light) and energy release. Our current research pursues two main strands: (i) synthesis and characterisation of novel energetic coordination compounds and (ii) photochemistry of nitrogen-rich covalent compounds. The potential applications of our research range from chemical energy storage to pyrotechnics, explosives, and propellants.

Energetic coordination compounds

Work in this area involves the exploration of preparative approaches toward new main-group element complexes bearing all-nitrogen or nitrogen-rich ligands. Specific systems we study are:

• polyazido complexes, such as [E(N3)6]- (E = P shown left)
• poly(tetrazolato) complexes
• polynitrato complexes

Research is directed towards the synthesis of new complexes and the study of their stability and reactivity and the derivation of structure-stability relationships.

Photochemistry and photophysics of nitrogen-rich covalent compounds

Photochemical transformations of high-energy compounds are not understood well. They offer interesting opportunities into studying the mechanism of decomposition of such compounds. In particular, we are interested in the photophysics and photochemistry of nitrogen-rich compounds, which are studied using a combination of Laser excitation and time-resolved infrared spectroscopy (a typical TRIR spectrum shown right).

Facilities

Apart from the excellent departmental instrumentation facilities for spectroscopy (NMR, IR, MS) and X-ray diffraction, which are vital for the characterisation of the nitrogen-rich materials, we also make regular use of a major national facitility for Laser spectroscopy in the UK, situated at the Rutherford Appleton Laboratory (Laser for Science Facility, LSF, http://www.clf.rl.ac.uk/).

General

Students and postdocs have the opportunity to engage in many aspects of our research, while developing greater expertise and interests in particular aspects of a specific project. Many projects involve the synthesis of organic or coordination compounds and energetic compounds, which sometimes will involve special techniques directed toward safe synthesis methods. Multinuclear NMR and IR spectroscopy and mass spectrometry are widely employed and extensive use is made of single crystal X-ray diffraction. Materials are often characterised by DSC and TGA methods. We use computational chemistry in order to support our understanding of thermal stability and predict properties of new energetic complexes. Collaborations are vital for our work and students have the opportunity to visit other research labs.

Publications

Books

Portius P (2002) Untersuchungen über die Reaktivität von Verbindungen des Germaniums in der Oxidationsstufe +2, Germanium-Pseudohalogenide und Germylin-Komplexe. Berlin: Weissensee-Verlag.

Journal articles

Westwater B, Lloyd H, Vitorica-Yrzebal I, Fong A, McMaster P, Sloan M, Coaker B, Pulham CR & Portius P (2020) Synthesis and characterization of the mixed-ligand coordination polymer Cu3Cl(N4C-NO2)2. Dalton Transactions.
Portius P, Bühl M, George MW, Grevels F-W & Turner J (2019) Structure and dynamics of iron pentacarbonyl. Organometallics. View this article in WRRO
Smallwood ZM, Davis MF, Hill JG, James LJR & Portius P (2019) Syntheses, Structures, and Infrared Spectra of the Hexa(cyanido) Complexes of Silicon, Germanium, and Tin. Inorganic Chemistry, 58(7), 4583-4591. View this article in WRRO
Campbell R, Konar S, Hunter S, Pulham C & Portius P (2018) Labile Low-Valent Tin Azides: Syntheses, Structural Characterization, and Thermal Properties.. Inorganic Chemistry, 57(1), 400-411. View this article in WRRO
Michalchuk AAL, Fincham PT, Portius P, Pulham CR & Morrison CA (2018) A Pathway to the Athermal Impact Initiation of Energetic Azides. The Journal of Physical Chemistry C, 122(34), 19395-19408. View this article in WRRO
Portius P & Davis M (2016) Synthesis of six-coordinate mono-, bis-, and tris(tetrazolato) complexes via [3 + 2] cycloadditions of nitriles to silicon-bound azido ligands. Dalton Transactions, 45(43), 17141-17152. View this article in WRRO
Portius P, Peerless B, Davis M & Campbell R (2016) Homoleptic Poly(nitrato) Complexes of Group 14 Stable at Ambient Conditions. Inorganic Chemistry, 55(17), 8976-8984. View this article in WRRO
Campbell R, Davis MF, Fazakerley M & Portius P (2015) Taming Tin(IV) Polyazides. Chemistry - A European Journal, 21(51), 18690-18698. View this article in WRRO
Peerless B, Keane T, Meijer AJHM & Portius P (2015) Homoleptic Low-Valent Polyazides of Group 14 Elements. Chemical Communications, 51(35), 7435-7438. View this article in WRRO
Portius P, Davis M, Campbell R, Hartl F, Zeng Q, Meijer AJHM & Towrie M (2013) Dinitrogen release from arylpentazole: a picosecond time-resolved infrared, spectroelectrochemical, and DFT computational study.. Journal of Physical Chemistry A, 117(48), 12759-12769. View this article in WRRO
Domene C, Portius P, Fowler PW & Bernasconi L (2013) Simulating the pyrolysis of polyazides: a mechanistic case study of the [[P(N3)6]- anion.. Inorg Chem, 52(4), 1747-1754.
Portius P & Davis M (2013) Recent developments in the chemistry of homoleptic azido complexes of the main group elements. Coordination Chemistry Reviews.
Portius P, Filippou A, Schnakenburg G, Davis M & Wehrstedt K-D (2011) Taming the Silicon Tetraazide Beast. Synfacts, 2011(03), 0348-0348.
Portius P, Filippou A, Schnakenburg G, Davis M & Wehrstedt K-D (2011) Taming the Silicon Tetraazide Beast. Synfacts, 2011(01), 0043-0043.
George MW, Hall MB, Portius P, Renz AL, Sun X-Z, Towrie M & Yang X (2011) Combined experimental and theoretical investigation into C-H activation of cyclic alkanes by Cp'Rh(CO)2 (Cp' = η5-C5H5 or η5-C5Me5).. Dalton Trans, 40(8), 1751-1757.
George MW, Hall MB, Jina OS, Portius P, Sun X-Z, Towrie M, Wu H, Yang X & Zaric SD (2010) Understanding the factors affecting the activation of alkane by Cp'Rh(CO)2 (Cp' = Cp or Cp*).. Proc Natl Acad Sci U S A, 107(47), 20178-20183.
Portius P, Filippou AC, Schnakenburg G, Davis M & Wehrstedt K-D (2010) Neutrale Lewis-Basen-Addukte des Siliciumtetraazids. Angewandte Chemie, 122(43), 8185-8189.
Portius P, Filippou AC, Schnakenburg G, Davis M & Wehrstedt K-D (2010) Neutral Lewis base adducts of silicon tetraazide.. Angew Chem Int Ed Engl, 49(43), 8013-8016.
Portius P & Davis M (2010) A new hexakis(isocyanato)silicate(IV) and the first neutral Lewis-base adducts of silicon tetraisocyanate.. Dalton Trans(2), 527-532.
Besora M, Carreón-Macedo J-L, Cowan AJ, George MW, Harvey JN, Portius P, Ronayne KL, Sun X-Z & Towrie M (2009) A combined theoretical and experimental study on the role of spin states in the chemistry of Fe(CO)5 photoproducts.. J Am Chem Soc, 131(10), 3583-3592.
Alamiry MAH, Boyle NM, Brookes CM, George MW, Long C, Portius P, Pryce MT, Ronayne KL, Sun XZ, Towrie M & Vuong KQ (2009) Unusually Slow Photodissociation of CO from (eta(6)-C6H6)Cr(CO)(3) (M = Cr or Mo): A Time-Resolved Infrared, Matrix Isolation, and DFT Investigation. ORGANOMETALLICS, 28(5), 1461-1468.
Portius P, Fowler PW, Adams H & Todorova TZ (2008) Experimental and theoretical characterization of the hexaazidophosphate(V) ion.. Inorg Chem, 47(24), 12004-12009.
Blake AJ, George MW, Hall MB, McMaster J, Portius P, Sun XZ, Towrie M, Webster CE, Wilson C & Zaric SD (2008) Probing the mechanism of carbon-hydrogen bond activation by photochemically generated hydridotris(pyrazolyl)borato carbonyl rhodium complexes: New experimental and theoretical investigations. ORGANOMETALLICS, 27(2), 189-201.
Sun X-Z, Portius P, Grills DC, Cowan AJ & George MW (2008) Cell design for picosecond time-resolved infrared spectroscopy in high-pressure liquids and supercritical fluids.. Appl Spectrosc, 62(1), 24-29.
Cowan AJ, Portius P, Kawanami HK, Jina OS, Grills DC, Sun X-Z, McMaster J & George MW (2007) Time-resolved infrared (TRIR) study on the formation and reactivity of organometallic methane and ethane complexes in room temperature solution.. Proc Natl Acad Sci U S A, 104(17), 6933-6938.
Ball GE, Brookes CM, Cowan AJ, Darwish TA, George MW, Kawanami HK, Portius P & Rourke JP (2007) A delicate balance of complexation vs. activation of alkanes interacting with [Re(Cp)(CO)(PF3)] studied with NMR and time-resolved IR spectroscopy.. Proc Natl Acad Sci U S A, 104(17), 6927-6932.
McMaster J, Portius P, Ball GE, Rourke JP & George MW (2006) Density functional theoretical studies of the Re-Xe bonds in Re(Cp)(CO) (PF3)Xe and Re(Cp)(CO)(2)Xe. ORGANOMETALLICS, 25(22), 5242-5248.
Ball GE, Darwish TA, Geftakis S, George MW, Lawes DJ, Portius P & Rourke JP (2005) Characterization of an organometallic xenon complex using NMR and IR spectroscopy.. Proc Natl Acad Sci U S A, 102(6), 1853-1858.
Filippou AC, Philippopoulos AI, Portius P & Schnakenburg G (2004) Halide substitution reactions of the germylidyne complexes trans-[X(dppe)(2)W Ge(eta(1)-Cp*)] (X = Cl, I; dppe = Ph2PCH2CH2PPh2; Cp* = C5Me5). ORGANOMETALLICS, 23(19), 4503-4512.
Portius P, Yang J, Sun X-Z, Grills DC, Matousek P, Parker AW, Towrie M & George MW (2004) Unraveling the photochemistry of Fe(CO)5 in solution: observation of Fe(CO)3 and the conversion between 3Fe(CO)4 and 1Fe(CO)4(Solvent).. J Am Chem Soc, 126(34), 10713-10720.
Kuimova MK, Alsindi WZ, Dyer J, Grills DC, Jina OS, Matousek P, Parker AW, Portius P, Sun XZ, Towrie M , Wilson C et al (2003) Using picosecond and nanosecond time-resolved infrared spectroscopy for the investigation of excited states and reaction intermediates of inorganic systems. Dalton Transactions, 2003(21), 3996-4006.
Filippou AC, Portius P, Philippopoulos AI & Rohde H (2003) Dreifachbindung zu Zinn: Synthese und Charakterisierung des Stannylidinkomplexes trans-[Cl(PMe3)4WSnC6H3-2,6-Mes2]. Angewandte Chemie, 115(4), 461-464.
Filippou AC, Portius P, Philippopoulos AI & Rohde H (2003) Triple bonding to tin: synthesis and characterization of the stannylyne complex trans-[Cl(PMe3)4W[triple bond]Sn-C6H3-2,6-Mes2].. Angew Chem Int Ed Engl, 42(4), 445-447.
Filippou AC, Portius P & Schnakenburg G (2003) The Hexaazidosilicate(IV) Ion: Synthesis, Properties, and Molecular Structure.. ChemInform, 34(2).
Filippou AC, Portius P & Schnakenburg G (2002) The hexaazidosilicate(IV) ion: synthesis, properties, and molecular structure.. J Am Chem Soc, 124(42), 12396-12397.
Filippou AC, Portius P & Philippopoulos AI (2002) Molybdenum and tungsten germylyne complexes of the general formula trans-X(dppe)(2)M=Ge-(eta(1)-Cp*)] (X = Cl, Br, I; dppe = Ph2PCH2CH2PPh2; Cp* = C5Me5): Syntheses, molecular structures, and bonding features of the germylyne ligand. ORGANOMETALLICS, 21(4), 653-661.
Filippou AC, Portius P, Winter JG & Kociok-Kohn G (2001) Stereoselective insertion of GeCl2 into tungsten-chlorine bonds of aminomethylene and aminocarbyne complexes. J ORGANOMET CHEM, 628(1), 11-24.
Filippou AC, Portius P & Jankowski C (2001) Aminomethylene complexes of molybdenum(IV) and tungsten(IV) bearing 1,2-dithiolato ligands. J ORGANOMET CHEM, 617(1), 656-670.
Filippou AC, Portius P, Neumann DU & Wehrstedt K-D (2000) Das Hexaazidogermanat(IV)-Ion – Synthesen, Strukturen und Reaktionen. Angewandte Chemie, 112(23), 4524-4527.
Filippou A, Portius P, Philippopoulos A, Kociok-Kohn G & Ziemer B (2000) Pentane and tetrahydrofuran solvates of trans-dichlorobis[1,2-ethanediyl-bis(diphenylphosphine)-P,P ']molybdenum(II). ACTA CRYSTALLOGR C, 56, E378-E379.
Filippou AC, Philippopoulos AI, Portius P & Neumann DU (2000) Synthese und Struktur der Germylinkomplexetrans-[X(dppe)2W≡Ge(η1-Cp*)] (X=Cl, Br, I) und Vergleich der W≡E-Bindungen (E=C, Ge) mit Dichtefunktionalrechnungen. Angewandte Chemie, 112(15), 2881-2884.
Filippou AC, Philippopoulos AI, Portius P & Neumann DU (2000) Synthesis and Structure of the Germylyne Synthesis and Structure of the Germylyne Complexes trans-[X(dppe)2WºGe(h1-Cp*)] and Comparison of the WºE Bonds (E = C, Ge) by Density Functional Calculations. Angew Chem Int Ed Engl, 39(15), 2778-2781.
Filippou AC, Portius P, Neumann DU & Wehrstedt KD (2000) The hexaazidogermanate(IV) ion: Syntheses, structures, and reactions. ANGEW CHEM INT EDIT, 39(23), 4333-4336.
Filippou AC, Portius P, Kociok-Kohn G & Albrecht V (2000) Oxidation of germanium(II) azides with HN3: a convenient route to six-co-ordinate triazidogermanium(IV) compounds. J CHEM SOC DALTON, 11, 1759-1768.
Filippou AC, Philippopoulos AI, Portius P & Neumann DU (2000) Synthesis and structure of the germylyne complexes trans-[X(dppe)(2)W Ge(eta(1)-Cp*)] (X = Cl, Br, I) and comparison of the W E bonds (E = C, Ge) by density functional calculations. ANGEW CHEM INT EDIT, 39(15), 2778-2781.
Filippou AC, Portius P & Kociok-Kohn G (1998) Germanium(II) azides: synthesis and crystal structure of Tp ' GeN3 [Tp ' = hydrotris(3,5-dimethylpyrazol-1-yl)borato]. CHEM COMMUN(21), 2327-2328.
Winter JG, Portius P, Kociok-Kohn G, Steck R & Filippou AC (1998) Insertion of Cp*GeCl into a tungsten-chlorine bond and crystal structures of the germylenes Cp*GeCl, [Cp*GeBr](2), and [Cp*Ge][BF4] (Cp* = pentamethylcyclopentadienyl). ORGANOMETALLICS, 17(19), 4176-4182.
Shipp J, Parker S, Spall S, Peralta-Arriaga SL, Robertson CC, Chekulaev D, Portius P, Turega S, Buckley A, Rothman R & Weinstein JA () Photocatalytic Reduction of CO₂ to CO in Aqueous Solution under Red-Light Irradiation by a Zn-Porphyrin-Sensitized Mn(I) Catalyst. Inorganic Chemistry.
Portius P, Meijer AJHM, Towrie M, Crozier BF & Schiager I () Picosecond time-resolved infrared spectroscopy of rhodium and iridium azides. Dalton Trans., 43(47), 17694-17702. View this article in WRRO
Michalchuk AAL, Trestman M, Rudic S, Portius P, Fincham PT, Pulham CR & Morrison C () Predicting the reactivity of energetic materials : an ab initio multi-phonon approach. Journal of Materials Chemistry A. View this article in WRRO

Chapters

Portius P, Adams M, Cross M & Roseveare T (2023) Synthesis, Structure and Reactivity of Energetic Nitrobis(Pyrazolyl)Benzenes, Future Developments in Explosives and Energetics (pp. 17-45). Royal Society of Chemistry
Speak T, Woolford S, Farrimond D, Christopher I, Barr A, Portius P & Tyas A (2023) Experimental Observation and Modelling of Contained Detonations of PE4: What is the Influence of Afterburn?, Future Developments in Explosives and Energetics (pp. 200-219). Royal Society of Chemistry
George MW & Portius P (2007) Studying Highly Reactive Organometallic Complexes with Infrared Spectroscopy: Matrix Isolation, Liquefied Noble Gases, Supercritical Fluids, and Time-resolved IR Spectroscopy, Comprehensive Organometallic Chemistry III (pp. 263-277). Elsevier
Portius P & George MW (2006) Studying Highly Reactive Organometallic Complexes with Infrared Spectroscopy: Matrix Isolation, Liquefied Noble Gases, Supercritical Fluids, and Time-resolved IR Spectroscopy In Crabtree R & Mingos M (Ed.), Comprehensive Organometallic Chemistry III: Volume 1: Introduction - Fundamentals Elsevier Science
Cowan A, Portius P, Sun X-Z, George MW, Towrie M & Ronayne K (2005) How does the strength of the Fe-Solvent bond affect the formation of 1Fe(CO)4(solvent)? In Wyborn B (Ed.), CCLRC Central Laser Facility, Annual Report 2004/2005 (pp. 119-120).
Portius P, Sun X-Z, Jina OS, Grills DC, George MW, Matousek P, Parker AW & Towrie M (2004) Monitoring the C-H Activation of methane by Rh(η5-C5H5)(CO)2 in solution at room temperature In Wyborn B (Ed.), CCLRC Central Laser Facility, Annual Report 2003/2004 (pp. 137-138). Council for the Central Laboratory of the Research Councils
Yang J, Portius P, Sun X-Z, Grills DC, George MW, Towrie M, Matousek P & Parker AW (2003) Photolysis of Fe(CO)5 studied by picosecond time-resolved infrared spectroscopy in conventional and supercritical fluids In Wyborn B (Ed.), CCLRC Central Laser Facility, Annual Report 2002/2003 (pp. 112-113). STFC

Conference proceedings papers

Portius P, James L, Peerless B, Smallwood Z & Crozier B (2017) Taming binary p-block azides with N-heterocyclic sigma-donors as precursors for the formation of nitrogen-rich tetrazolato complexes. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 254 View this article in WRRO
Portius P, Crozier B, James L, Smallwood Z & Campbell R (2016) Nitrogen-rich complexes of p-block elements : highly endothermic polytetrazolates and polyazides. Abstracts of Papers of the American Chemical Society, Vol. 252. Philadelphia, PA, USA, 21 August 2016 - 25 August 2016. View this article in WRRO
Weinstein JA, Sazanovich IV, Delor M, Scattergood PA, Meijer AJHM, Portius P, Greetham G, Parker AW & Towrie M (2013) Ultrafast photoinduced charge-separation in molecular systems: Time-resolved IR, transient 2DIR, and controlling the rates and the pathways by vibrational perturbation. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, Vol. 245
Kuimova MK, Alsindi WZ, Dyer J, Grills DC, Jina OS, Matousek P, Parker AW, Portius P, Sun XZ, Towrie M , Wilson C et al (2003) Using picosecond and nanosecond time-resolved infrared spectroscopy for the investigation of excited states and reaction intermediates of inorganic systems. DALTON TRANSACTIONS(21) (pp 3996-4006)
Portius P () Synthesis, structure and reactivity of energetic nitrobis(pyrazolyl)benzenes. Proceedings of the International Explosives Conference
Portius P, Speak T, Woolford S, Barr A, Tyas A & Portius P () Experimental observation and modelling of contained detonations of PE4: What is the influence of afterburn?. Proceedings of the International Explosives Conference

Patents

Portius P & Filippou AC () Synthesis and use of silicon polyazides and nitrogen-containing azidosilicate salts as candidate energetic materials. 102 25 175.4 Appl. 01 Jan 1970.

Reports

Portius P, Davis M & Towrie M (2011) CCLRC Central Laser Facility, Rutherford Appleton Laboratory Annual Report, Lasers for Science Facility Programme – Chemistry, 2010-2011
Portius P, Weinstein JA, Davis M & Sazanovich IV () CCLRC Central Laser Facility, Rutherford Appleton Laboratory Annual Report, Lasers for Science Facility Programme – Chemistry, 2009-2010

Teaching interests: Spectroscopic Characterisation

Teaching activities

Undergraduate and postgraduate taught modules

Chemistry and the World Around Us (Level 1): The chemistry of explosives.
This module provides a basic overview of the chemistry of explosive compounds: their formulation, behaviour, properties and applications.
Characterisation using Spectroscopy (Level 2)
This course introduces a variety of spectroscopic techniques which are used for the characterisation of molecules and complexes in inorganic chemistry, and shows how these methods can be used (on their own and in combination) to provide information about the structure of molecules and properties of inorganic compounds. In particular, mass spectrometry (EI, MALDI, ESI), UV/visible absorption spectroscopy, NMR spectroscopy (31P, 19F, 11B, 109Rh etc.) and EPR spectroscopy (S = ½) are included and the concept of spectroscopic timescale is discussed.
Inorganic Materials (Level 3)
The course provides an overview of synthesis, structures and properties of selected inorganic materials. A survey of different methods of synthesis of materials is provided. The structures and applications of zeolites and related silicate materials are presented. The preparation and applications of semiconductor materials are introduced.
Chemistry of High-Energy Materials (Level 4)
Energetic materials science is at the heart of propellants, explosives and pyrotechnics. It provides the tools and concepts to determine and understand the structure and properties of energetic structures and their dynamic behaviour on timescales ranging from seconds to nanoseconds. This course will introduce the theory and application of energetic materials, their synthesis and characterisation, the current models describing their initiation and decomposition, and examples of applications.

Support Teaching:

Tutorials: Level 2 Inorganic Chemistry
Skills for Success: Database Project.
Level 3 Literature Review

Laboratory Teaching:

Level 3 Inorganic Laboratories
Level 3 Research Project
Level 4 Research Project