School of Chemistry, UNSW

Marcus L. Cole

B.Sc., Ph.D., Cardiff
Senior Lecturer
E-mail: m.cole@unsw.edu.au

BIOGRAPHICAL DETAILS

Born 1976, Graduate of Cardiff University (B.Sc.(Hons I), University Medal, 1998, Ph.D., 2001). Royal Society Postdoctoral Fellow, Monash University (2002). ARC Postdoctoral Research Fellow, Monash University, and Risdon Grimwade Lecturer, Trinity College, University of Melbourne (2003-2004). Lecturer, University of Adelaide (2004-2007). Appointed Senior Lecturer UNSW (2007).

RESEARCH INTERESTS

Our research focuses on the study of rare or unknown metallohydride and organometallic species in terms of their fundamental properties and synthetic utility. We have several collaborations with researchers overseas and interstate. The following projects are representative of our studies:

(i) Heavy group 13 hydrides (M = Al, Ga, In, Tl) and halohydrides

The hydride chemistries of Al and Ga are well established, while those of indium and thallium are nascent and non-existent respectively.

Our focus on mixed halide-hydrides, or halohydrides, emanates from their enhanced stability relative to the respective metal trihydrides. Partial halogenation results in a modified M-H bond polarity, distinct reactivity, and potential as precursors to functionalised low valent (Mn⁺, n < 3) compounds by reductive dehydrogenation. The latter represents the underlying basis for our approach to hydrogen uptake, storage and stimulated release.

Novel group 13 hydrides and their reactions

(ii) N-heterocyclic carbenes (NHC) in catalysis

The utility of NHCs in catalysis is well documented. The catalytic activity of NHC supported species typically exceeds that of traditional phosphane systems, however there are some noteworthy downsides: (A) the steric range of NHCs is small relative to phosphanes, especially at the 'upper-end' of the spatial regime, (B) chiral NHC supported species have struggled to emulate the stereoselectivity of chrial phosphanes in asymmetric catalysis.

We are addressing these drawbacks with the preparation of the first N-2,6-terphenyl NHCs (drawback (A)) and chiral NHCs with atropisomeric 2-biaryls at nitrogen (drawback (B)) and catalytic studies thereof.

N-heterocyclic carbenes

(iii) The stabilisation of low oxidation state group 3 complexes

We are interested in unearthing and developing paths to low oxidation state group 3 complexes (Mn+, n < 3). At this time the sub-trivalent chemistries of Sc and Y are rare and poorly understood. As per low valent group 13 species isolated in project (i), we are interested in the reactivity of such species, particularly as reagents for reductive coupling reactions.

low oxidation state scandium complex

PROFESSIONAL INTERESTS

Member, Royal Australian Chemical Institute and Royal Society of Chemistry.
South Australian RACI Inorganic Division Representative (2007).
Organising committee member for the 5th Australian Organometallic Discussion Conference - OZOM5.

COLLABORATIONS

Dr Jonathan C. Morris, University of Adelaide, South Australia. Atropselective Synthesis of Biaryls, Chiral NHCs and Asymmetric Catalysis
Prof. Hans-Jeorg Himmel, University of Heidelberg, Germany. Photochemical Studies of the Halometallanes of Group 13.
Prof. Steven P. Nolan, University of St Andrews, Scotland, UK. NHC Complexes and Synthetic Applications.

TRAINING AND OUTPUT

Our research utilises a suite of solution and solid-state molecular structure characterisation methods including multinuclear NMR spectroscopy and single crystal X-ray structure determination. Students gain broad experience in modern inorganic and organic synthetic techniques, and the handling of pyrophoric and highly air/moisture sensitive compounds. Students complete their doctorate, which typically includes a research placement in Europe, within 3-4 years with 4-10 refereed research publications and several conference papers.

SELECTED PUBLICATIONS

Tertiary Amine and N-Heterocyclic Carbene Coordinated Haloalanes - Synthesis, Structure and Application, Sean G. Alexander, Marcus L. Cole and Craig M. Forsyth, Chem. Eur. J., 2009, DOI: 10.1002/chem.200900365.
Bulky Triazenide Complexes of Alumino- and Gallohydrides. Sean G. Alexander, Marcus L. Cole, Craig M. Forsyth, Samantha K. Furfari and Kristina Konstas, Dalton Trans., 2009, DOI: 10.1039/b817397d.
Preparation of a Super Bulky Silver N-Heterocyclic Carbene Complex, Sean G. Alexander, Marcus L. Cole and Jonathan C. Morris, New J. Chem., 2009, DOI: 10.1039/b821368b.
Hydride-bromide exchange at an NHC - A new route to brominated alanes and gallanes, Sean G. Alexander, Marcus L. Cole, Samantha K. Furfari and Marc Kloth, Dalton Trans., 2009, DOI: 10.1039/b821367d.
The reactivity of N-heterocyclic carbenes and their precursors with [Ru₃(CO)₁₂]. Michael I. Bruce, Marcus L. Cole, Ricky S. C. Fung, Craig M. Forsyth, Matthias Hilder, Peter C. Junk and Kristina Konstas, Dalton Trans., 2008, 4118.
Lewis Base Adducts of Heavier Group 13 Halohydrides - Not Just Aspiring Trihydrides!, Sean G. Alexander and Marcus L. Cole, Eur. J. Inorg. Chem., 2008, 4493.
The synthesis of a dichloroalane complex and its reaction with an α-diimine, Sean G. Alexander, Marcus L. Cole, Matthias Hilder, Jonathan C. Morris and Joanna B. Patrick, Dalton Trans., 2008, 6361.
Alkali metal bis(aryl)formamidinates: A study of coordinative versatility. M. L. Cole and P. C. Junk, Chem. Commun., Feature Article, 2007, 1579.
Steric modulation of coordination number and reactivity in the synthesis of lanthanoid(III) formamidinates. M. L. Cole, G. B. Deacon, C. M. Forsyth, P. C. Junk and K. Konstas, Chem. Eur. J., 2007, 13, 8082.
The synthesis of a sterically hindered samarium(II) bis(amidinate) and conversion to its homoleptic trivalent congener. M. L. Cole, P. C. Junk, Chem. Commun., 2005, 2695.
Synthesis and Characterization of Thermally Robust Amidinato Group 13 Hydride Complexes. M. L. Cole, C. Jones, P. C. Junk, M. Kloth, A. Stasch, Chem. Eur. J., 2005, 11, 4482.
Controlled Decomposition of an Indium Trihydride Adduct: Synthesis and characterisation of the First Mixed Oxidation State Indium Sub-Halide Complex Anion, [In₅Br₈(quinuclidine)₄]^-. M. L. Cole, C. Jones, M. Kloth, Inorg. Chem., 2005, 44, 4909.