Staff Profile

Background

1962 ARCS and BSc, Imperial College London, after research project on NMR of As, Sb and Bi triethyls, with Dr. Dennis Evans

1965 PhD,  University of Cambridge, on fluorocarbon-nitrogen chemistry, e.g. of (CF₃)₂NBr, with Prof. Harry Emeléus

1965-66 Postdoctoral research, University of Washington, Seattle, on non-metal - fluorine chemistry, e.g. of SF₅OF, with Prof. George Cady

1966-67 Postdoctoral research, University of Bristol, on fluorocarbon-transition metal complexes, with Prof. F.G.A. Stone

1967-2006 Lecturer in Inorganic Chemistry, University of Newcastle

1967-82 Preparative research on novel small halogenocarbon-nitrogen molecules, e.g. CCl₃NO

1982-2006 Preparative and solution ³¹P NMR research on novel phosphorus-chalcogenide cage molecules, e.g. P₅S₂I

2006 Appointed Guest Member of Staff, Chemistry in the School of Natural Sciences

1992-present  Ab initio calculations on phosphorus chalcogenide molecules, to identify species made and to characterise reaction routes

1974-present  Devising software for chemists, for use in undergraduate teaching or in research (see Software available for download)

2002-present  Web page development, particularly for showing molecular models (for a how-to-do-it guide and a sample portfolio, see Web Pages using Jmol)

Administrative Responsibilities

1982-2015 Chemistry Undergraduate Database Officer

1997-2006 Chairman of the Undergraduate Board of Examiners in Chemistry

2002-present  Researching and reporting annual statistical surveys of undergraduate progression and attainment

Research Interests

STUDIES OF CAGE MOLECULES CONTAINING PHOSPHORUS, BY SOLUTION NMR SPECTROSCOPY
Some of the most interesting chemistry of the lighter non-metals concerns their cage and ring compounds, and for phosphorus in low oxidation states this is particularly important, ranging from white phosphorus itself, through polyphosphane cages, selenides, sulfides and oxides, to imides. Synthetic chemistry here has been particularly assisted by the availability of phosphorus nuclear magnetic resonance spectroscopy: in contrast to carbon, phosphorus is almost uniquely placed as a skeletal atom with 100% abundance of a spin-½, reasonably NMR-sensitive, nucleus. Even for new compounds on the borderline of stability between molecular and polymeric structures, and hence incapable of isolation, phosphorus NMR can provide certain identification, provided there are enough coupled nuclei in the cage, and enough is known about the rules relating NMR chemical shifts and coupling constants to cage structure.

We have made, in solution, new compounds P₄S₃XY containing exocyclic substituents (X and Y range from halide, through pseudohalide, thiolate, or amino groups, to phosphino groups or hydride). By measuring and completely fitting their complex phosphorus NMR spectra, we have developed the required detailed knowledge of the dependence of NMR parameters on substituent effects and cage geometry. This has enabled us to identify new phosphorus-rich skeletons P₅S₂X and even new phosphorus halides such as P₇X₃. In contrast, we have also investigated phosphorus-poor molecules P₃Se₄X and P₂Se₅, in which selenium replaces phosphorus at cage apices, in collaboration with the preparative chemistry group of Prof. R. Blachnik of the University of Osnabrück, Germany. If exocyclic substituents are chiral, diastereomers can be made which allow steric effects to be studied specifically. Ab initio calculations of structures and NMR shieldings allow assignment of spectra to individual isomers or even rotamers.

Seclected Publications
[1] B.W. Tattershall and E.L. Sandham, J. Chem. Soc., Dalton Trans. 2001, 1834-1840.

[2] B. W. Tattershall, R. Blachnik and A. Hepp, J.Chem.Soc., Dalton Trans. 2000, 2551-2558.

[3] B. W. Tattershall, E. L. Sandham and W. Clegg, J.Chem.Soc., Dalton Trans. 1997, 81-87.

[4] R. Blachnik, K. Hackmann and B. W. Tattershall, Polyhedron 1996, 15, 1415-27.

• Tattershall BW, Geneux NS, Holmes KE, Hargreaves MD, McMorrow G. Insertion of Methylthiirane into the P-I Bonds of alpha-P4S3I2. Zeitschrift fuer Anorganische und Allgemeine Chemie 2009, 635(13-14), 2222-2229.
• Tattershall BW, Holmes KE, Tweedy C, Valks GC. alpha-tetraphosphorus trichalcogenide diamides and imides containing both sulfur and selenium. Zeitschrift für anorganische und allgemeine Chemie 2008, 634(10), 1703-1710.
• Tattershall BW, Knight JG, Andrews MJ. Phosphorus NMR and ab initio modelling of P-N bond rotamers of a sterically crowded chiral β-P4S3 diamide. Zeitschrift fur Anorganische und Allgemeine Chemie 2007, 633(9), 1442-1450.
• Tattershall BW, Knight JG, Andrews MJ, Booth CL. Phosphorus NMR characterisation of P-N bond rotamers of a α-P₄S₃ amide with a conformationally constrained chiral substituent. Zeitschrift fur Anorganische und Allgemeine Chemie 2006, 632(3), 425-432.
• Tattershall BW. Assignment of phosphorus NMR parameters to absolute configurations in chiral phosphorus sulfide cage compounds, using Ab initio methods. Zeitschrift fur Anorganische und Allgemeine Chemie 2005, 631(9), 1627-1632.
• Tattershall BW, Houghton RW, Martin DJ. Polycyclic phosphorus sulfide compounds containing chiral amido or imido substituents. Zeitschrift fur Anorganische und Allgemeine Chemie 2004, 630(12), 1991-1998.
• Tattershall BW, Sandham EL. Interdependence of phosphorus-31-selenium-77 NMR coupling constants in bicyclic phosphorus selenide compounds. Journal of the Chemical Society, Dalton Transactions 2001, (12), 1834-1840.
• Tattershall BW, Blachnik R, Hepp A. Phosphorus NMR and ab initio study of pentaphosphorus dichalcogenide halides 1. Journal of the Chemical Society, Dalton Transactions 2000, (15), 2551-2558.