Chitnis Lab Research Publications Group Facilities Contact
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Welcome to the Chitnis lab!

We are coming to Dalhousie University in beautiful Halifax, Nova Scotia starting July 2018 and have positions available for undergraduate and graduate students. Research in the group will focus on making tailored inorganic compounds for fundamentally interesting and useful chemistry.

Using the principles of coordination chemistry and our synthetic expertise, we aim to rationally design and study molecules that fall within three broad categories:

More details are given below. Please get in touch if you are interested in any of these topics and would like to discuss further.

Group News

♦ Saurabh will give two talks at CSC-2017 in Toronto

Monday 1720 h: Macromolecules Containing Metal and Inorganic Elements symposium (abstract)

Tuesday 1720 h: Main Group Transformations and Catalysis symposium (abstract)

♦ Group website goes live - May 2017

Research areas

Vernazza

Redox-active main group centres

Reversible redox chemistry is generally considered to be the realm of transition metal systems, which contain energetically proximate frontier molecular orbitals. This unique electronic structure can be finely tuned using coordination chemistry, which forms the foundation of modern transition metal catalysis. However, some of the most valuable catalytic transformations also require elements (e.g. Pd, Pt, Rh, Ru, Au) whose prohibitive costs and/or potential toxicity are limiting factors in their utility. Besides a handful of examples, p-block elements are virtually unexplored as platforms for redox catalysis because they usually undergo irreversible oxidation-state changes. To unlock their potential in this area, we seek to discover the fundamental rules governing changes in frontier orbital energies at main group centres as a function of geometry and ligand environment. We will then use this knowledge to design affordable and non-toxic main group systems for cross-coupling catalysis.

Cinque Terre

Lewis superacids

Strong Lewis acids such as AlCl3 play an essential role as catalysts in industrial and academic chemistry. They are also precursors to weakly coordinating anions that permit the study of highly electrophilic cations. We are interested in the synthesis of new classes of neutral and cationic Lewis superacids (more acidic than SbF5) for fundamental studies involving binding of non-classical donors in main group coordination chemistry (H2, Si-H, N2, COx, NOx, olefins etc.), and for applications in catalysis and anion sensing. Some of these Lewis acids will also be converted to weakly coordinating anions, which are important tools in organometallic chemistry, and may find applications as electrolyte components in batteries. In order to broaden the utility of these compounds, we will devise strategies to make Lewis superacids that can be handled under ambient conditions. This effort will draw upon emerging concepts in Lewis acid chemistry such as steric frustration and cooperative Lewis acidity.

Monterosso

Inorganic polymers and clusters

Polymers and clusters derived from elements other than carbon are fascinating because their unique electronic structure leads to properties that are in accessible for organic compounds. For example, polysilanes and polystannanes exhibit σ-bond conjugation and act as molecular wires. We are interested in preparing polymers with a backbone derived from the group 15 elements, which would feature a redox active lone pair in the main chain. The fundamental chemistry of such materials is entirely unknown. We are also interested in main group homopolyatomic cations - the positively-charged versions of Zintl anions. More specifically, we will investigate binary or ternary mixtures of well-defined ions as a route to tailor-made molecular clusters of semiconducting intermetallics. These will shed light upon the properties of bulk seminconducting phases and will themselves exhibit interesting reactivity.

Publications

Before Dalhousie:

2017 S. S. Chitnis, H. A. Sparkes, N. E. Pridmore, V. T. Annibale, A. M. Oliver and I. Manners, 'Addition of a Cyclophosphine to Nitriles: An Inorganic "Click" Reaction Featuring Protio-, Organo-, and Main Group Catalysis', Angew. Chem. Int. Ed., 2017, In press.
S. S. Chitnis, R. A. Musgrave, H. A. Sparkes, N. E. Pridmore, V. T. Annibale, and I. Manners, 'Influence of Ring Strain and Bond Polarization on the Ring Expansion of Phosphorus Homocycles', Inorg. Chem., 2017, 56(8), 4521-4537.
2016 S. S. Chitnis, K. Vos, N. Burford, R. McDonald, and M. J. Ferguson, 'Distinction Between Coordination and Phosphine Ligand Oxidation: Interactions of Di- and Tri-phosphines with Pn3+ (Pn = P, As, Sb, Bi)', Chem. Commun., 2016, 685-688.
K. L. Bamford, S. S. Chitnis, R. L. Stoddard, J. S. McIndoe, and N. Burford, 'Bond Fission in Monocations: Diverse Fragmentation Pathways for Phosphinophosphonium Cations', Chem. Sci., 2016, 7, 2544-2552.
S. Yogendra, S. S. Chitnis, F. Hennersdorf, M. Bodensteiner, R. Fischer, N. Burford, and J. J. Weigand, 'Condensation Reactions of Chlorophosphanes with Chalcogenides', Inorg. Chem., 2016, 55, 1854-1860.
A. P. M. Robertson, S. S. Chitnis, S. Chhina, H. J. Cortes, B. O. Patrick, H. A. Jenkins, and N. Burford, 'Complexes of Trimethylsilyl Trifluoromethanesulfonate with Nitrogen, Oxygen and Phosphorus Donors', Can. J. Chem., 2016, 94, 424-429.
2015 S. S. Chitnis, A. P. M. Robertson, N. Burford, B. O. Patrick, R. McDonald, and M. J. Ferguson, 'Bipyridine Complexes of E3+ (E = P, As, Sb, Bi): Strong Lewis Acids, Sources of E(OTf)3 and Synthons for EI and EV Cations', Chem. Sci., 2015, 6, 6545-6555.
S. S. Chitnis, N. Burford, J. J. Weigand, and R. McDonald, 'Reductive Catenation of Phosphine-Antimony Complexes', Angew. Chem. Int. Ed., 2015, 54, 7828-7832.
S. S. Chitnis, A. P. M. Robertson, N. Burford, J. J. Weigand, and R. Fischer, 'Synthesis and Reactivity of Cyclo-tetra(stibinophosphonium) Tetracations: Redox and Coordination Chemistry of Phosphine-Antimony Complexes', Chem. Sci., 2015, 6, 2559-2574.
A. P. M. Robertson, S. S. Chitnis, H. Jenkins, R. McDonald, M. J. Ferguson, and N. Burford, 'Establishing the Coordination Chemistry of Antimony(V) Cations: Systematic Assessment of Ph4Sb(OTf) and Ph3Sb(OTf)2 as Lewis Acceptors', Chem. Eur. J., 2015, 21, 7902-7913.
S. S. Chitnis, and N. Burford, 'Phosphine complexes of lone-pair bearing acceptors', Dalton Trans., 2015, 44, 17-29.
2014 S. S. Chitnis, M. Whalen, and N. Burford, 'Influence of Charge and Coordination Number on Bond Dissociation Energies, Distances and Vibrational Frequencies for the Phosphorus-Phosphorus Bond', J. Am. Chem. Soc., 2014, 136, 12498-12506.
S. S. Chitnis, N. Burford, R. McDonald, and M. J. Ferguson, 'Prototypical Phosphine Complexes of Antimony(III)', Inorg. Chem., 2014, 53(10), 5359-5372.
2013 S. S. Chitnis, N. Burford, A. Decken, and M. J. Ferguson, 'Coordination Complexes of Bismuth Triflates with THF and Diphosphine Ligands', Inorg. Chem., 2013, 52(12), 7242-7248.
S. S. Chitnis, Y-Y. Carpenter, N. Burford, R. McDonald and M. J. Ferguson, 'Assembly of a cyclo-tetrastibinotetraphosphonium Tetracation by Reductive Elimination', Angew. Chem. Int. Ed., 2013, 52(18), 4863-4866.
S. S. Chitnis, N. Burford, and M. J. Ferguson, '2,2-Bipyridine Complexes of Antimony: Sequential Fluoride Ion Abstraction from SbF3 by Exploiting the Fluoride Ion Affinity of Me3Si+', Angew. Chem. Int. Ed., 2013, 52(7), 2042-2045.
2012 E. MacDonald, L. Doyle, S. S. Chitnis, U. Werner-Zwanziger, N. Burford, and A. Decken, 'Me3P Complexes of P-block Lewis Acids SnCl4, [SnCl3]1+, and [SnCl2]2+', Chem. Commun., 2012, 48(64), 7922-7924.
S. S. Chitnis, E. MacDonald, N. Burford, U. Werner-Zwanziger, and R. McDonald, 'P-P Menschutkin Preparation of Prototypical Phosphinophosphonium Salts', Chem. Commun., 2012, 48(59), 7359-7361.
2011 S. S. Chitnis, B. Peters, E. Conrad, N. Burford, R. McDonald, and M. J. Ferguson, 'Structural Diversity for Phosphine Complexes of Stibenium and Stibinidenium Cations', Chem. Commun., 2011, 47, 12331-12333.
2009 F. Lollmahomed, W. J. Leigh, L. A. Huck, S. S. Chitnis, and C. R. Harrington, 'Time-Resolved Spectroscopic Studies of the Reactivities of Transient Germylenes in Methanol and Tetrahydrofuran Solution', Organometallics, 2009, 28(5), 1484-1494.

Group

Boss

Saurabh S. Chitnis, Ph. D.

Group Leader

Ph. D. University of Victoria (2015, Neil Burford)
PDF - University of Bristol (2017, Ian Manners)

The group will begin operations in July 2018 at Dalhousie University. Members will gain hands-on experience in synthetic inorganic chemistry and catalysis, including the use of Schlenk and high-vacuum lines, dryboxes, NMR/Mass/IR/Raman spectroscopy techniques, X-ray crystallography, and electrochemistry. In addition, group members will be part of a department that boasts internationally-recognized experts in computational chemistry, catalysis, and battery technology. If you are interested in joining us for undergraduate or graduate research, please contact Saurabh by email.

We are also seeking postdoctoral researchers with intentions of applying for fellowships to join us. In addition to external sources (e.g. NSERC, Banting, etc.), Dalhousie also offers the prestigious Killam Postdoctoral Fellowships for outstanding candidates to undertake two years of research.

Halifax is located on the east coast of Canada and is the capital of Nova Scotia. It is a major hub of economic, political, scientific and cultural activities in eastern Canada and offers all the benefits of a major urban centre while maintaining the beauty and feel of a coastal city. It is one of the most affordable cities of its size in Canada and well-connected to destinations in Europe and North America. Click here to discover what Halifax offers and here to learn more about Dalhousie University.

If you are considering joining us for your graduate studies, click here to find the necessary information about important dates and the numerous funding opportunities offered by the university.

Feel free to contact Saurabh if you would like additional information!

Facilities

Installation of the laboratory will begin in July 2018.

Once equipped we will have grease-free Schlenk and high vacuum lines, dryboxes, electrochemical equipment, a Rigaku X-ray diffractometer, and a full suite of glassware for synthetic inorganic chemistry. We will have access to instruments in the departmental NMR facility, the Institute for Research in Materials, and the Mass Spectrometry facility. The university is also part of a High Performance Computing consortium which offers several software packages for quantum chemical calculations. An on-site glassblower provides access to customized scientific glassware.

Email

Prospective students, postdoctoral researchers, and anyone else interested in our research is invited to get in touch by email: saurabh.chitnis@dal.ca