The University of Oxford

The Goicoechea Group

Department of Chemistry

The Chemical Research Lab

Welcome

Welcome to the Goicoechea Group website!

Our research is focused on the chemistry of environmentally abundant, non-toxic main-group elements (e.g. silicon and phosphorus). This ranges from purely fundamental studies (such as the synthesis of elusive small molecules and reactive intermediates), to more applied fields. The common feature to all of our research is that it involves the synthesis of previously unknown molecules and solids. We are interested in compounds of the main-group elements in unusual oxidation states, p-block species exhibiting multiple bonds, main-group clusters and transition-metal organometallic compounds. We are particularly fascinated by molecules that defy conventional rules for bonding and that exhibit unusual reactivity.

Recent years have witnessed a renaissance of main-group cluster chemistry as the solution-phase reactivity of the “naked” polyanions of groups 14 and 15 has been explored.[1,2] The use of transition metal reagents (particularly open-shell species) has resulted in the isolation of a series of novel species in which the metal atoms play an essential role in the stabilization of large, otherwise unattainable geometries.[3,4] Figure 1 shows two such clusters. The remarkable pentagonal prismatic geometry exhibited by [Fe@Ge10]3– makes it the first species of its kind to be isolated.[3] Furthermore, the structure of [Ru@Ge12]3– contrasts dramatically with the known deltahedral or approximately deltahedral geometries of [M@Pb12]2– (M = Ni, Pd, Pt) and [Mn@Pb12]3– and is a result of extensive delocalization of electron density from the transition-metal centre onto the cage.[4]

Figure 1
Figure 1. [Fe@Ge10]3– (left) and [Ru@Ge12]3– (right): Two classes of unprecedented endohedral three-connect clusters.

In addition to the activation chemistry of the clusters, simple salt metathesis of metal halides has yielded a range of coordination compounds bearing intact Zintl clusters. For example, reaction of FeCl2 with K3P7 in the presence of a proton source affords an iron centre sandwiched by two protonated heptaphosphide cages, which can be viewed as a Zintl analogue of ferrocene (see Figure 2.).[5] There are multiple different binding modes for both group 14 and 15 clusters, which can be pre-ordained by a judicious choice of metal centre, and these give rise to a multitude of products that can be further functionalised.

The ability of Zintl ions to undergo nucleophilic and electrophilic substitution allows for their integration into cluster-assembled materials. The clusters isolated to date represent the first steps in a nascent area of chemistry where many interesting breakthroughs await.

Figure 2
Figure 2. Synthesis of [Fe(HP7)2]2– from FeCl2 and K3P7.

References

[1] Sevov, S. C.; Goicoechea, J. M. Organometallics, 2006, 25, 5678.

[2] Turbervill, R. S. P.; Goicoechea, J. M. Chem. Rev., 2014, 114, 10807.

[3] Zhou, B.; Denning, M. S.; Kays, D. L.; Goicoechea, J. M. J. Am. Chem. Soc., 2009, 131, 2802.

[4] Espinoza-Quintero, G.; Duckworth, J. C. A.; Myers, W. K.; McGrady, J. E.; Goicoechea, J. M. J. Am. Chem. Soc., 2014, 136, 1210.

[5] Knapp, C. M.; Large, J. S.; Rees, N. H.; Goicoechea, J. M. Chem. Commun., 2011, 47, 4111.

Studies carried out by our research group have yielded a route towards the synthesis of bulk quantities of the 4,4′-bipyridyl radical anion and the dianion in high yields.[1] We have characterised these species by single crystal X-ray diffraction in Na(en)(4,4′-bipy)· and Na2(en)2(4,4′-bipy)2−, respectively. We have further extended these studies to include the radical and dianionic forms of the 2,2′ and 2,4′ bipyridine isomers.[2] From a coordination chemistry viewpoint, the 2,2′-bipyridyl radical and dianion provides a unique ligand for the synthesis of novel coordination complexes of the first row transition metals with interesting magnetic properties.[3,4]

We have also studied the chemical reduction of N-heterocyclic carbene complexes of first row transition metals[5,6] and the group 12 metals (see Figure 1.)[7] which have provided a viable route towards the formation of ditopic carbanionic NHC ligands.[8] This remarkable reactivity has resulted in the isolation of novel complexes of backbone functionalised NHCs and provides the possibility to investigate the subsequent chemistry such sterically and electronically altered NHCs. We have gone on to synthesise the potassium salt of a ditopic carbanionic NHC and have demonstrated its use as a synthon for the generation of novel polar organometallic species of the group 12 and 14 metals.[9] Research aimed at exploiting the chemistry of the free carbene site for the activation of small molecules and supramolecular chemistry is ongoing.

Figure 1
Figure 1. A homoleptic trigonal planar Hg(II) anion bearing three ditopic carbanionic N-heterocyclic carbenes.

References

[1] Denning, M. S.; Irwin, M.; Goicoechea, J. M. Inorg. Chem., 2008, 47, 6118.

[2] Gore-Randall, E.; Irwin, M.; Denning, M. S.; Goicoechea, J. M. Inorg. Chem., 2009, 48, 8304.

[3] Irwin, M.; Doyle, L. R.; Krämer, T.; Herchel, R.; McGrady, J. E.; Goicoechea, J. M. Inorg. Chem., 2012, 51, 12301.

[4] Irwin, M.; Krämer, T.; McGrady, J. E.; Goicoechea, J. M. Inorg. Chem., 2011, 50, 5006.

[5] Musgrave, R. A.; Turbervill, R. S. P.; Irwin, M.; Goicoechea, J. M. Angew. Chem. Int. Ed., 2012, 51, 10832.

[6] Musgrave, R. A.; Turbervill, R. S. P.; Irwin, M.; Herchel, R.; Goicoechea, J. M. Dalton Trans., 2014, 43, 4335.

[7] Waters, J. B.; Turbervill, R. S. P.; Goicoechea, J. M. Organometallics, 2013, 32, 5190.

[8] Waters, J. B.; Goicoechea, J. M. Coord. Chem. Rev., 2014, 293-294, 80.

[9] Waters, J. B.; Goicoechea, J. M. Dalton Trans., 2014, 43, 14239.

The isolobal relationship between a methine moiety (C–H) and a phosphorus atom allows for the synthesis of interesting phosphorus-containing variants of organic molecules. This has led to phosphorus being referred to as the “carbon-copy”. Following on from the successful transition metal-mediated activation of [E7]3– (E = P, As),[1,2] we were prompted to explore the activation of [P7]3– using unsaturated organic fragments. This led to the synthesis of a range of 1,2,3-triphospholides (and their heavier arsenic congeners), which are related to the ubiquitous cyclopentadienyl ligand.[3–5]

Figure 1

We have also reported the activation of [P7]3– by ambient pressures of carbon monoxide to form the phosphaethynolate anion, PCO, as the [K(18-crown-6)]+ salt.[6] This has opened an exciting new avenue of research in the group, as at the time of publication there were few reports in the chemical literature on this heavier congener of the omnipresent cyanate anion, NCO. We have since reported the cycloaddition chemistry of PCO towards heteroallenes to form phosphorus-containing heterocycles,[6] and its reactivity towards strained main group systems.[7]

Furthermore, by analogy with Wöhler’s paradigm-shifting synthesis of urea in 1828, the reaction of PCO with ammonium salts was found to yield the unprecedented phosphinecarboxamide.[8] This inorganic analogue of urea is a rare example of an air-stable primary phosphine, and its ligand properties have been explored.[9] We believe these molecules are of fundamental interest and harbour enormous potential as building blocks for organophosphorus reagents and phosphorus-containing polymers. Work on this topic is currently on-going.

References

[1] Knapp, C, M.; Westcott, B. H.; Raybould, M. A. C.; McGrady, J. E.; Goicoechea, J. M. Angew. Chem. Int. Ed., 2012, 51, 9097.

[2] Knapp, C. M.; Westcott, B. H.; Raybould, M. A. C.; McGrady, J. E.; Goicoechea, J. M. Chem. Commun., 2012, 48, 12183.

[3] Turbervill, R. S. P.; Goicoechea, J. M. Chem. Commun., 2012, 48, 6100.

[4] Turbervill, R. S. P.; Jupp, A. R.; McCullough, P. S. B.; Ergöçmen, D.; Goicoechea, J. M. Organometallics, 2013, 32, 2234.

[5] Turbervill, R. S. P.; Goicoechea, J. M. Inorg. Chem., 2013, 52, 5527.

[6] Jupp, A. R.; Goicoechea, J. M. Angew. Chem. Int. Ed., 2013, 52, 10064.

[7] Robinson, T. P.; Cowley, M. J.; Scheschkewitz, D.; Goicoechea, J. M. Angew. Chem. Int. Ed., 2015, 54, 683.

[8] Jupp, A. R.; Goicoechea, J. M. J. Am. Chem. Soc., 2013, 135, 19131.

[9] Geeson, M. B.; Jupp, A. R.; McGrady, J. E.; Goicoechea, J. M. Chem. Commun., 2014, 50, 12281.

Group
Members

Year

The group in 2016 – 2017 The group in 2015 – 2016 The group in 2014 – 2015 The group in 2013 – 2014 The group in 2012 – 2013 The group in 2011 – 2012 The group in 2010 – 2011 The group in 2009 – 2010 The group in 2008 – 2009

Jose Goicoechea

Click below to see description
    • Jordan, now in the fourth year of his D.Phil. after having completed his Part II in 2012-2013, is continuing research on ditopic carbanionic N-heterocyclic carbenes and in the use of NHCs for the stabilisation of low valent main group complexes. However we’re not so sure as he spends most of his time at his desk rather than in the lab, although arguably this is now justified as he should be writing his thesis. He claims he likes to bake and go cycling but probably will be found playing pool in the pub instead. He is the best IT Rep the group has ever seen!

    • David is a third year D.Phil. student researching geometry constrained main-group complexes for the activation of small molecules. Originally from Hong Kong, David completed his undergraduate studies at Durham University. He drinks smoothie and non-alcohols. He runs a lot outside the lab and wants to finish an Ironman competition someday.

    • Stefans is a Part II student from St Catz, he comes from Latvia, a small country by the Baltic sea. Apart from studying bulky amido-tin chlorides, Stefans likes experimenting with cooking, but always ends up with a piece of coal instead of a steak and setting off the firealarm.

    • We’ve tried to put together some sentences about him, but found this really hard to do because outside the lab he is practically not defined… there is just not much noteworthy to mention. Alex is another post-doc in the Goicoechea group. The last thing he got done was working on singlet biradicaloids in the group of Prof. Axel Schulz at the University of Rostock, Germany. Since arriving in the UK, he indulges in drinking tepid tea from morning to afternoon. Occasionally, he even tries to learn about and get used to the peculiarities of living on this side of the Channel.

    • Jose carried out his undergraduate degree at the University of Zaragoza in his home country of Spain. After a brief stint as an Erasmus student at the University of Cambridge with Professor Paul Raithby, he began his Ph.D work at the University of Bath under the supervision of Mike Whittlesey. He completed his thesis in 2003 on the synthesis and reactivity of novel water-soluble ruthenium (II) phosphine complexes. A postdoctoral position with Professor Slavi Sevov at the University of Notre Dame followed (2003-2006) exploring the reactivity of anionic deltahedral Zintl ions in solution.
      Jose was appointed to a University Lectureship in Inorganic Chemistry at the University of Oxford on October 1st 2006.

    • Geve is a Part II student from University College who is working on synthesising and characterising various phosphinecarboxamides.

    • Currently in the second year of her DPhil, Erica came to the U.K. from Brazil to pursue her dream of investigating the reactivity of the PCO anion. A passionate tango dancer, Erica secretly hopes Corey will one day ask her to be his dance partner. Erica also enjoys baking and thus holds the title of group baking rep, responsible for providing baked goods at birthdays, holidays, leaving parties and any other occasion people can make up. Her arch nemesis is the raisin.

    • Tom is a postdoctoral researcher in the group. He completed his postgraduate studies at the University of Bath working with Prof. Paul Raithby and Dr. Andrew Johnson developing novel heterometallic polyyne complexes. Out of the lab he spends his time chasing wildlife around the countryside with his camera (but is reluctant to take pictures of the lab for the website) and watching Arsenal get progressively worse every year (but still better than Tottenham). Now he is married he doesn’t need to think up original excuses for not coming to the pub on Fridays.

    • Harry is a Part II student from Keble studying main group N-heterocyclic carbene complexes. He plays the cornet (no ice cream involved) in a local brass band, and will happily talk about cryptic crosswords to anyone who will listen, which is approximately no-one.

    • Corey “could you give me five minutes, please?” Smith is a part II student from Balliol studying constrained geometry main group compounds. He is the undisputed dance champion of the group, with boogying abilities ranging from waltz to hip-hop and everything between. Corey’s other interests include the colour pink, Formula 1, and (Judd) Trump.

    • Dan is the newest member of the group and so he still has an air of mystery about him. All we’ve deciphered so far is that from his home town of Carlisle, he first travelled to Leeds to do his masters and has now arrived in Oxford to do his DPhil with the group. His interests appear to be drinking, going to the gym and playing Settlers of Catan. Hopefully as we get to know him better, we’ll find some more interesting hobbies.

    • Chris (why eat solid food?) is a Part II student from Wadham studying the reactivity of the Phosphathioethynolate anion. Chris doesn’t eat like a normal person, instead he gets his nutrition in the form of weirdly coloured supplement powders he adds to water. He invites us to play a stimulating game every morning of ‘guess the colour of my drink’, and it’s the highlight of everyone’s day. He has also been extraordinarily proactive with his lab work after his Macbook breaking (RIP) in his first week. Our thoughts are with him during this grave time (pun intended).

    • We’ve tried to put together some sentences about him, but found this really hard to do because outside the lab he is practically not defined… there is just not much noteworthy to mention. Alex is another post-doc in the Goicoechea group. The last thing he got done was working on singlet biradicaloids in the group of Prof. Axel Schulz at the University of Rostock, Germany. Since arriving in the UK, he indulges in drinking tea from morning to afternoon. Occasionally, he even tries to learn about and get used to the peculiarities of living on this side of the Channel.

    • Andy is a fourth year DPhil researching phosphorus analogues of common nitrogen-containing organic species, particularly the PCO anion and phosphinecarboxamide: an inorganic analogue of urea. He is the group’s Language Rep, which has been tested to its limits on conferences in Bulgaria, Dublin, Germany and recently in Hong Kong. Although his attempts at replicating accents are in earnest, they often come across as slightly confused. That being said, his German accent based on the Three Little Pigs from Shrek is peerless.

    • Jose carried out his undergraduate degree at the University of Zaragoza in his home country of Spain. After a brief stint as an Erasmus student at the University of Cambridge with Professor Paul Raithby, he began his Ph.D work at the University of Bath under the supervision of Mike Whittlesey. He completed his thesis in 2003 on the synthesis and reactivity of novel water-soluble ruthenium (II) phosphine complexes. A postdoctoral position with Professor Slavi Sevov at the University of Notre Dame followed (2003-2006) exploring the reactivity of anionic deltahedral Zintl ions in solution.
      Jose was appointed to a University Lectureship in Inorganic Chemistry at the University of Oxford on October 1st 2006.

    • Tom is a Part II student from Univ studying ditopic carbanionic N-heterocyclic carbenes. Tom loves bikes. Tom stares at photos of new bikes when he’s not riding them. Permanently disappointed when it’s not him that Claire is calling after but the other Tom. He also has an incredibly sweet tooth, and you can always bank on him having a secret stash of sweets to cheer you up when your chemistry might not be going to plan.

    • Jess is a Part II student from Magdalen. Whilst she’s meant to be investigating geometrically constrained group 14 complexes, she is, in fact, focused on just how many weeks will pass before she can do any actual chemistry. Much to the amusement of the rest of the group, she has commandeered a footstool so she can reach the top shelves. She has also (unofficially) taken on the role of ‘baking rep’ after the great success of her brownies brought in during her first week.

    • Jordan, now a third year D.Phil. student in the group after having completed his Part II in 2012-2013, is continuing research on ditopic carbanionic N-heterocyclic carbenes, however we’re not so sure as he spends most of his time at his desk rather than in the lab. He claims he likes to bake, play guitar and go cycling but probably will be found playing pool in the pub instead. He is the best IT Rep the group has ever seen!

    • Érica is a first year DPhil student from Brazil. She completed her undergraduate course at Universidade Federal de Minas Gerais, where she used to work with Supramolecular Chemistry. She enjoys dancing and practicing Krav Maga in her free time.

    • Claire is a Part II student from Queen’s researching the activation of small molecules by constrained geometry phosphorous compounds. In her first week in the group, Claire demonstrated her immense boxing prowess by breaking the door to the lab, although we suspect boxing is a front to allow her to leave the lab early on Thursdays.

    • Tom is a postdoctoral researcher in the group. He completed his postgraduate studies at the University of Bath working with Prof. Paul Raithby and Dr. Andrew Johnson developing novel heterometallic polyyne complexes. Out of the lab he spends his time chasing wildlife around the countryside with his camera (but is reluctant to take pictures of the lab for the website) and watching Arsenal get progressively worse every year (but still better than Tottenham). Now he is married he doesn’t need to think up original excuses for not coming to the pub on Fridays.

    • David is a second year D.Phil. student researching geometry constrained main-group complexes for the activation of small molecules. Originally from Hong Kong, David completed his undergraduate studies at Durham University, and is the latest member of the group. He has already shown such an incredible knack for growing crystals that he often throws them away simply to spite those who struggle in this department. Despite not being engaged, the group are already planning an extravagant stag party, largely to David’s embarrassment.

    • Andy is a third year D.Phil. researching organophosphorus reagents derived from the activation of group 15 Zintl clusters, particularly the PCO anion and phosphinecarboxamide: an inorganic analogue of urea. Having survived his Part II year, he enjoys no longer being the one asking the most stupid questions in the lab. He is also the group’s “Language Rep.”, which was tested to its limits on recent conferences in Bulgaria and Dublin. This appointment is particularly baffling as another member of the group can legitimately speak seven languages. His self appointed role of “Rep-Rep” however has gone to his head.

    • David is a first year D.Phil. student researching geometry constrained main-group complexes for the activation of small molecules. Originally from Hong Kong, David completed his undergraduate studies at Durham University, and is the latest member of the group. He has already shown such an incredible knack for growing crystals that he often throws them away simply to spite those who struggle in this department. Despite not being engaged, the group are already planning an extravagant stag party, largely to David’s embarrassment.

    • Jordan, now a second year D.Phil. student in the group after having completed his Part II in 2012-2013, is continuing research on ditopic carbanionic N-heterocyclic carbenes, however we’re not so sure as he spends most of his time at his desk rather than in the lab. He claims he likes to bake, play guitar and go cycling but probably will be found playing pool in the pub instead. He is the best IT Rep the group has ever seen!

    • Tom is a postdoctoral researcher in the group. He completed his postgraduate studies at the University of Bath working with Prof. Paul Raithby and Dr. Andrew Johnson developing novel heterometallic polyyne complexes. Out of the lab he spends his time chasing wildlife around the countryside with his camera and watching Arsenal get progressively worse every year (but still better that Tottenham). Now he is married he doesn’t need to think up original excuses for not coming to the pub on Fridays.

    • Jose carried out his undergraduate degree at the University of Zaragoza in his home country of Spain. After a brief stint as an Erasmus student at the University of Cambridge with Professor Paul Raithby, he began his Ph.D work at the University of Bath under the supervision of Mike Whittlesey. He completed his thesis in 2003 on the synthesis and reactivity of novel water-soluble ruthenium (II) phosphine complexes. A postdoctoral position with Professor Slavi Sevov at the University of Notre Dame followed (2003-2006) exploring the reactivity of anionic deltahedral Zintl ions in solution.
      Jose was appointed to a University Lectureship in Inorganic Chemistry at the University of Oxford on October 1st 2006.

    • Oli is a Part II student from University College, exploring the synthesis of novel main-group complexes of ditopic carbanionic N-heterocyclic carbenes, although we are unsure that he actually knows what these words mean. He can often be found doing press ups in the write up area, but on the few occasions he ventures into the lab he can found hoarding the group’s glassware or eyeing up the blow torch, which has reignited (pun intended) his childhood fascination with fire. Outside the lab, Oli is all about fitness. His regimented diet and gym routine has seen him rise to the upper echelons of the Triathlon Society, where he currently sits as captain. Has been quoted as calling himself “The Third Brownlee”.

    • Jamie is a Part II student from St Catherine’s College, researching chemical reactivity of group 14 and 15 Zintl ion cages towards organometallic species. After arriving late, Jamie’s only hope for staying awake is his regular large bottle of coke and his addiction to the SportBible. His recent success of NMRing a starting material and chanting “it’s clean” was a real milestone in Jamie’s chemistry career. Outside the lab, Jamie enjoys kicking cage like structures around a football pitch with his friends from Catz before marking his territory around Oxford. Jamie’s moves on the dancefloor are second to none and he regularly “Bumps ‘N Grinds” his product into the Schlenk line.

    • James is a Part II student from Keble College, exploring the use of phosphinecarboxamides as precursors to photoinitiators. After spending most of the morning waxing his hair, James may venture into the lab where he has a SMASHING time dancing around to German Mashups and cleaning up broken bits of NMR tubes. When not in the lab, he can most often be found at the University Club bar proudly telling all in listening range of his commitment to the University Pool Team, and of his recent discovery of the Iffley Road “Gym”, where he has been known to occasionally do weights - does he even lift? Yes, he does.

    • Gaby is from Mexico and completed an undergraduate course at Universidad de las Américas, Puebla. She is in the fourth year of her D.Phil. She is researching the reactivity of group 14 & 15 Zintl anions towards organometallic complexes. She enjoys playing drums, capoeira and sculpting marble figures of legendary Mexican singers in her free time.

    • Dan is a Part II student from LMH, researching geometry constrained main-group complexes for the activation of small molecules. Affectionately known as “Rosie”, it is unknown whether this nickname is a nod to his last name or a reference to his flowing locks. In the lab, Dan often takes a “one-step forward, two steps back” approach, but this could be a ploy to get attention from his post-doc supervisor Tom. Outside of lab hours, he is considered something of a BNOC in the online world as Vice-President of the Oxford e-Sports Society.

    • Michael is a Part II student from LMH, carrying out a joint research project with Professor John McGrady. He has recently crept Gollum-like out of the dark recesses of the PTCL basement into the airy CRL labs to start the synthesis portion of his Part II. Despite enjoying his start in an actual lab, he has been heard to say that he misses watching football whilst pretending to compute complex molecular structures. Little is known about his life outside lab hours, although it is rumoured that the film “Magic Mike” is based on the out of lab exploits of Mr Connolly. He remains decidedly coy on the subject.

    • Gaby is from Mexico and completed an undergraduate course at Universidad de las Américas, Puebla. She is in the third year of her D.Phil. She is researching the reactivity of group 14 & 15 Zintl anions towards organometallic complexes. She enjoys playing drums, capoeira and sculpting marble figures of legendary Mexican singers in her free time.

    • Andy is a second year D.Phil. student researching phosphorus-containing molecules derived from group 15 Zintl clusters, particularly that of the PCO anion. Having survived his Part II year in the group he now enjoys (mostly) no longer being the one asking the most stupid questions in the lab. Outside of the lab Andy has no extracurricular activities and despite having kissed the Blarney Stone has absolutely no chat either.

    • Mike is a Part II student from Merton College, carrying out a joint research project with Professor John McGrady. He is computationally investigating the recently synthesised phosphinecarboxamide and some related structures. When not sat in front of a computer, Mike spends his time playing squash and rugby - or persuading the group to let him loose in the lab.

    • Rob is an EPSRC funded Doctoral Prize holder. He has worked in most of the group’s research areas during either his Part II or DPhil studies. His current research is focused on extending his DPhil work on the the reactivity of group 15 cluster anions towards unsaturated organic substrates. He enjoys hiking, running, and taking a curious interest in the affairs of the New Orleans Saints.

    • Dave is a Part II student from St John’s and is currently investigating unsaturated group 15 ring systems. Dave prides himself in not having an inside voice and so can be heard even if you’re not in the CRL with him. He enjoys tennis, football, Sul Ki Do and parkour, and would much prefer to be doing sport than drinking. Many would argue Dave doesn’t understand how to be a student.

    • Jose carried out his undergraduate degree at the University of Zaragoza in his home country of Spain. After a brief stint as an Erasmus student at the University of Cambridge with Professor Paul Raithby, he began his Ph.D work at the University of Bath under the supervision of Mike Whittlesey. He completed his thesis in 2003 on the synthesis and reactivity of novel water-soluble ruthenium (II) phosphine complexes. A postdoctoral position with Professor Slavi Sevov at the University of Notre Dame followed (2003-2006) exploring the reactivity of anionic deltahedral Zintl ions in solution.
      Jose was appointed to a University Lectureship in Inorganic Chemistry at the University of Oxford on October 1st 2006.

    • Tom is the postdoctoral researcher within the group. He completed his postgraduate studies at the University of Bath working with Prof. Paul Raithby and Dr Andrew Johnson developing novel heterometallic polyyne complexes. When not in the Lab he’s usually travelling to or from the Lab and can commonly be seen shouting expletives at the electronic notice board at Oxford station. Outside the tyranny of train travel he’s often chasing wildlife around the countryside with his camera or making cakes to test on the group.

    • Jordan, now a first year D.Phil. student in the group after having completed his Part II in the group last year, is continuing research on N-heterocyclic carbenes and dicarbenes, however we’re not so sure as he spends most of his time at his desk rather than in the lab. He claims he likes to bake, play guitar and go cycling but probably will be found in the pub instead.

    • Izzy is a Part II student from New College, researching the activation of group 15 Zintl ions under the supervision of Gaby. When not in the lab, she can generally be found at the ice rink until the small hours of the morning, training for the only acceptable sort of hockey. Izzy also enjoys playing the violin and flute, as well as eating large amounts of food.

    • Gemma is a Part II student at Trinity investigating the reactivity of the 2-phosphaethynolate anion. When not in the lab she can be found on a netball court or in the kitchen pretending to be on the Great British Bake Off. Occasionally she can be spotted with a camera in hand if you wait long enough.

    • Lajoy is a Part II student from St John’s College, researching the reactivity of carbanionic carbenes under Jordan’s supervision. As the newest member of ‘Team Carbene’, Lajoy can often be seen growing ampoule-crushingly large crystals to match her ampoule-crushingly large jewellery. She spends her free time either studying French, or shimmying her troubles away in a Zumba class (or five).

    • Bethan is a Part II from St Peter’s College who is investigating the formation and reactivity of 1,2,3-triphospholide anions, amongst other things that don’t work. One of her keen passions in life is delaying making carrot cake for the longest time possible. Predictions are estimated at one year.

    • Rob is an EPSRC funded Doctoral Prize holder. He has worked in most of the group’s research areas during either his Part II or DPhil studies. His current research is focused on extending his DPhil work on the the reactivity of group 15 cluster anions towards unsaturated organic substrates. He enjoys hiking, running, and taking a curious interest in the affairs of the New Orleans Saints.

    • Andy is a second year D.Phil. student researching phosphorus-containing molecules derived from group 15 Zintl clusters, particularly that of the PCO anion. Having survived his Part II year in the group he now enjoys (mostly) no longer being the one asking the most stupid questions in the lab. Outside of the lab Andy has no extracurricular activities and despite having kissed the Blarney Stone has absolutely no chat either.

    • Jose carried out his undergraduate degree at the University of Zaragoza in his home country of Spain. After a brief stint as an Erasmus student at the University of Cambridge with Professor Paul Raithby, he began his Ph.D work at the University of Bath under the supervision of Mike Whittlesey. He completed his thesis in 2003 on the synthesis and reactivity of novel water-soluble ruthenium (II) phosphine complexes. A postdoctoral position with Professor Slavi Sevov at the University of Notre Dame followed (2003-2006) exploring the reactivity of anionic deltahedral Zintl ions in solution.
      Jose was appointed to a University Lectureship in Inorganic Chemistry at the University of Oxford on October 1st 2006.

    • Ben is a Part II from Teddy Hall, researching Group 15 Zintl chemistry under Caroline’s supervision. When in the lab he enjoys sabotaging the group’s glassware by sticking shut all the Schlenk taps, whilst outside the lab he enjoys the freely flowing beer-taps of Oxford’s many pubs, as well as occasionally swimming and cycling.

    • Jordan, now a first year D.Phil. student in the group after having completed his Part II in the group last year, is continuing research on N-heterocyclic carbenes and dicarbenes, however we’re not so sure as he spends most of his time at his desk rather than in the lab. He claims he likes to bake, play guitar and go cycling but probably will be found in the pub instead.

    • Gaby is from Mexico and completed an undergraduate course at Universidad de las Américas, Puebla. She is in the third year of her D.Phil. She is researching the reactivity of group 14 & 15 Zintl anions towards organometallic complexes. She enjoys playing drums, capoeira and sculpting marble figures of legendary Mexican singers in her free time.

    • Jack is a Part II from New, doing a joint project with John McGrady. Little is known about his identifying characteristics, because he seems to enjoy spending his time in the dank, dark depths of the ICL dungeon more than in the sunny climes of S11 in the CRL.

    • Caroline, a fourth year D.Phil researcher, is from Corpus Christi College and is working with Group 15 Zintl ions, continuing from her Part II project with this group. When not thinking about Chemistry she enjoys eating chocolate and dominating Muay Thai tournaments while dreaming about one day saving the world.

    • Binbin entered Selwyn College, Cambridge in 2003 and completed her undergrad degree in Natural Sciences in 2007. She is now a fifth year D.Phil student researching the solution reactivity of group 14 Zintl anions towards a series of organometallic complexes. When not thinking about science she enjoys reading, watching films, listening to music, cooking and renaissance agricultural farming.

    • Phil - who has an alter-ego called Brian - is a Part II from St Catherine’s. He is working on investigating the reactivity of group 15 Zintl ions with unsaturated compounds under Rob’s eagle eye. If nobody else is looking, he likes to break as much glassware as he can. When he is not at the lab or the river, he enjoys cooking, obscure Radio 4 programs, and having drunken arguments with Park End DJs who refuse to play Glee songs.

    • Becca, affectionately known as Muzzlechops, is a Part II from Oriel and is keenly researching low valent organometallic compounds under Mark’s exacting yet precise supervision. When not in labs, which does seem to be most of the time, she can be found miming in the college choir, getting messy with other women on a rugby pitch or increasing her vast collection of vintage (pimp) coats.

    • Rob is an EPSRC funded Doctoral Prize holder. He has worked in most of the group’s research areas during either his Part II or DPhil studies. His current research is focused on extending his DPhil work on the the reactivity of group 15 cluster anions towards unsaturated organic substrates. He enjoys hiking, running, and taking a curious interest in the affairs of the New Orleans Saints.

    • Jose carried out his undergraduate degree at the University of Zaragoza in his home country of Spain. After a brief stint as an Erasmus student at the University of Cambridge with Professor Paul Raithby, he began his Ph.D work at the University of Bath under the supervision of Mike Whittlesey. He completed his thesis in 2003 on the synthesis and reactivity of novel water-soluble ruthenium (II) phosphine complexes. A postdoctoral position with Professor Slavi Sevov at the University of Notre Dame followed (2003-2006) exploring the reactivity of anionic deltahedral Zintl ions in solution.
      Jose was appointed to a University Lectureship in Inorganic Chemistry at the University of Oxford on October 1st 2006.

    • Mark is from Oriel College and previously completed a Part II with the group. He is now a fourth year D.Phil researcher and enjoys the increased power and potential for corruption this affords him. He is an avid fan of mountain biking, endurance nocturnal mole watching, photography and sport spectating. Preferably from a sofa. He is researching highly reduced organic systems and is also meant to be responsible for this website.

    • Caroline, a fourth year D.Phil researcher, is from Corpus Christi College and is working with Group 15 Zintl ions, continuing from her Part II project with this group. When not thinking about Chemistry she enjoys eating chocolate and dominating Muay Thai tournaments while dreaming about one day saving the world.

    • Andy is a second year D.Phil. student researching phosphorus-containing molecules derived from group 15 Zintl clusters, particularly that of the PCO anion. Having survived his Part II year in the group he now enjoys (mostly) no longer being the one asking the most stupid questions in the lab. Outside of the lab Andy has no extracurricular activities and despite having kissed the Blarney Stone has absolutely no chat either.

    • Melissa is a Part II from LMH, doing a joint project with the McGrady Bunch. Nobody knows why she spends most of her time locked in the ICL basement, but we reckon it is because she finds opening doors inherently difficult. At least it stops her melting more expensive equipment. Keen to waste more people’s money, she then pulls freshers dodgy pints in the college bar. In her free time, she enjoys dancing, rowing (just for the crew dates), and shark taxonomy.

    • Gaby is from Mexico and completed an undergraduate course at Universidad de las Américas, Puebla. She is in the third year of her D.Phil. She is researching the reactivity of group 14 & 15 Zintl anions towards organometallic complexes. She enjoys playing drums, capoeira and sculpting marble figures of legendary Mexican singers in her free time.

    • Laurence is working under Mark on transition metal complexes with reduced hetero-aromatic ligands. Though a man of few words, he is positively debaucherous when it comes to dry ice/ acetone baths. Other indulgences include classical music, guitar, and underground gangsta rap.

    • Binbin entered Selwyn College, Cambridge in 2003 and completed her undergrad degree in Natural Sciences in 2007. She is now a fifth year D.Phil student researching the solution reactivity of group 14 Zintl anions towards a series of organometallic complexes. When not thinking about science she enjoys reading, watching films, listening to music, cooking and renaissance agricultural farming.

    • Rob is an EPSRC funded Doctoral Prize holder. He has worked in most of the group’s research areas during either his Part II or DPhil studies. His current research is focused on extending his DPhil work on the the reactivity of group 15 cluster anions towards unsaturated organic substrates. He enjoys hiking, running, and taking a curious interest in the affairs of the New Orleans Saints.

    • Jose carried out his undergraduate degree at the University of Zaragoza in his home country of Spain. After a brief stint as an Erasmus student at the University of Cambridge with Professor Paul Raithby, he began his Ph.D work at the University of Bath under the supervision of Mike Whittlesey. He completed his thesis in 2003 on the synthesis and reactivity of novel water-soluble ruthenium (II) phosphine complexes. A postdoctoral position with Professor Slavi Sevov at the University of Notre Dame followed (2003-2006) exploring the reactivity of anionic deltahedral Zintl ions in solution.
      Jose was appointed to a University Lectureship in Inorganic Chemistry at the University of Oxford on October 1st 2006.

    • Mark is from Oriel College and previously completed a Part II with the group. He is now a fourth year D.Phil researcher and enjoys the increased power and potential for corruption this affords him. He is an avid fan of mountain biking, endurance nocturnal mole watching, photography and sport spectating. Preferably from a sofa. He is researching highly reduced organic systems and is also meant to be responsible for this website.

    • Amy is a Part II from Hertford College, now working as the most important member of Team Zintl. Her research is focused on Zintl Phase Analogues of Transition Metal Metallocene Complexes. Her recent hero is Eduard Zintl and her talents include forgetting to turn on Argon gas and testing solvent effects with her face. Outside of the lab, she enjoys road cycling and having dinner parties, when not accidentally spending weekends in the pub after meaning to go for a cheeky pint.

    • Charlie recently joined the group as a part II, and is the key member of Team Zintl. This year he has the pleasure of working on Zintl ion complexes of the lanthanides, Actinides and group 10 transition metals. In his spare time he is preparing to take on the beer mat flipping world record having secured funding from Jose. So far he has successfully flipped 23 beer mats, his aim is to achieve 50 by the end of this year. Charlie also enjoys playing squash, lacrosse and having a good night out with friends.

    • Caroline, a fourth year D.Phil researcher, is from Corpus Christi College and is working with Group 15 Zintl ions, continuing from her Part II project with this group. When not thinking about Chemistry she enjoys eating chocolate and dominating Muay Thai tournaments while dreaming about one day saving the world.

    • Pete has joined the group this year as a Part II from Magdalen. His work is focusing on the synthesis and reactivity of boron functionalised group 15 clusters. He has the highly sought after position of disposable glove stock monitor. When the glove stock is assured he may be found playing badminton, falling out of planes or finding suitable roofs on which to store livestock.

    • Charlotte ‘CJ’ Jackson has joined the Goicoechea group as a Part II from St Johns this year. Despite demonstrating bowling prowess, her lab talents include bin fires and celite showers. She can otherwise be found playing hockey, cricket, netball or as the ‘token’ girl in the football team.

    • Mark completed a D.Phil on the intercalation chemistry of fullerenes under the supervision of Professor M. J. Rosseinsky. Outside interests include cricket, swimming, running, ice skating and amateur dramatics.

    • Belinda’s work is largely split into two categories, the first covers her childhood fascination with the reactions and compounds of bipyridine. The second area is concerned with human behaviour under stress, specifically the addition of air to the glovebox and its effect on the group.

    • Joe, a Part II from Worcester, is supposed to be working on a project involving Group 15 Zintl ions but instead is embarking on a mission to break the entire lab’s glassware. Outside of the lab you’ll probably find him playing cricket or occasionally playing football (for which he has gained a violent reputation), while also being keen to watch any sort of sport on TV.

    • Binbin entered Selwyn College, Cambridge in 2003 and completed her undergrad degree in Natural Sciences in 2007. She is now a fifth year D.Phil student researching the solution reactivity of group 14 Zintl anions towards a series of organometallic complexes. When not thinking about science she enjoys reading, watching films, listening to music, cooking and renaissance agricultural farming.

    • Rob is an EPSRC funded Doctoral Prize holder. He has worked in most of the group’s research areas during either his Part II or DPhil studies. His current research is focused on extending his DPhil work on the the reactivity of group 15 cluster anions towards unsaturated organic substrates. He enjoys hiking, running, and taking a curious interest in the affairs of the New Orleans Saints.

    • Jose carried out his undergraduate degree at the University of Zaragoza in his home country of Spain. After a brief stint as an Erasmus student at the University of Cambridge with Professor Paul Raithby, he began his Ph.D work at the University of Bath under the supervision of Mike Whittlesey. He completed his thesis in 2003 on the synthesis and reactivity of novel water-soluble ruthenium (II) phosphine complexes. A postdoctoral position with Professor Slavi Sevov at the University of Notre Dame followed (2003-2006) exploring the reactivity of anionic deltahedral Zintl ions in solution.
      Jose was appointed to a University Lectureship in Inorganic Chemistry at the University of Oxford on October 1st 2006.

    • Caroline, a fourth year D.Phil researcher, is from Corpus Christi College and is working with Group 15 Zintl ions, continuing from her Part II project with this group. When not thinking about Chemistry she enjoys eating chocolate and dominating Muay Thai tournaments while dreaming about one day saving the world.

    • Mark is from Oriel College and previously completed a Part II with the group. He is now a fourth year D.Phil researcher and enjoys the increased power and potential for corruption this affords him. He is an avid fan of mountain biking, endurance nocturnal mole watching, photography and sport spectating. Preferably from a sofa. He is researching highly reduced organic systems and is also meant to be responsible for this website.

    • Mark completed a D.Phil on the intercalation chemistry of fullerenes under the supervision of Professor M. J. Rosseinsky. Outside interests include cricket, swimming, running, ice skating and amateur dramatics.

    • David was a chemist at Univ. No further information is known about him at this time. Our condolences go out to his friends and family.

    • Binbin entered Selwyn College, Cambridge in 2003 and completed her undergrad degree in Natural Sciences in 2007. She is now a fifth year D.Phil student researching the solution reactivity of group 14 Zintl anions towards a series of organometallic complexes. When not thinking about science she enjoys reading, watching films, listening to music, cooking and renaissance agricultural farming.

    • Mark is from Oriel College and previously completed a Part II with the group. He is now a fourth year D.Phil researcher and enjoys the increased power and potential for corruption this affords him. He is an avid fan of mountain biking, endurance nocturnal mole watching, photography and sport spectating. Preferably from a sofa. He is researching highly reduced organic systems and is also meant to be responsible for this website.

    • This is where we would typically have a bit about each group member and their interests, hobbies, distinguishing features, fingerprints, next of kin, blood type etc. The passage of text in this section is unnecessarily and uncharacteristically elongated and overly verbose so that I can ascertain the effectiveness of the word wrapping of this text in this text field.

    • Jose carried out his undergraduate degree at the University of Zaragoza in his home country of Spain. After a brief stint as an Erasmus student at the University of Cambridge with Professor Paul Raithby, he began his Ph.D work at the University of Bath under the supervision of Mike Whittlesey. He completed his thesis in 2003 on the synthesis and reactivity of novel water-soluble ruthenium (II) phosphine complexes. A postdoctoral position with Professor Slavi Sevov at the University of Notre Dame followed (2003-2006) exploring the reactivity of anionic deltahedral Zintl ions in solution.
      Jose was appointed to a University Lectureship in Inorganic Chemistry at the University of Oxford on October 1st 2006.

    • Caroline, a fourth year D.Phil researcher, is from Corpus Christi College and is working with Group 15 Zintl ions, continuing from her Part II project with this group. When not thinking about Chemistry she enjoys eating chocolate and dominating Muay Thai tournaments while dreaming about one day saving the world.

    • Ed is an accident waiting to happen. He spends most of his time reducing things, often Jose to tears. This work is a continuation of Mark Irwin’s work from the previous year.

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Facilities

The Goicoechea Group is based in lab S11 in the Chemistry Research Laboratory and benefits from the state-of-the-art facilities the building has to offer. In addition, we have access to resources available in the Inorganic Chemistry Laboratory building and in other departments within the University of Oxford. These slides provide a flavour of the frequently used group and communal resources.

The Lab - S11

Many of the materials that the group works with are highly air- and moisture-sensitive, requiring special equipment to manipulate them in order to avoid contact with the air. All of the laboratory fume hoods are fitted with dual manifold Schlenk lines so that attached vessels can be purged of air and water prior to their contact with reagents.

Schlenk Lines

Weighing of air-sensitive reagents and products is routinely carried out in the group’s glove-box which has a computer controlled nitrogen atmosphere. Both water and oxygen levels are maintained below 0.1 ppm. The glovebox also contains dehydrated solvents which permits small scale, sensitive reactions to be carried out overnight, within the glove-box itself.

Glovebox

Zintl phase starting materials such as or K3P7 or K4Ge9 are directly synthesised by the combination of elements in sealed niobium tubes that are heated in a high temperature furnace for several days. The tubes are sealed in the absence of oxygen using a custom built arc-welder with a chamber that can be evacuated and filled with argon. Niobium is used to avoid side reactions taking place with the metal vessel at the high temperatures. The tubes are placed in larger silica glass ampoules which are evacuated before sealing with a glass blowing torch.

Arc Welding

Dry solvents are essential for the types of reactions undertaken by the group. The communal MBraun SPS800 solvent drying systems provide ten dry solvents in a readily accessible fashion, which can be used directly without further purification.

Solvent Drying

The primary structural characterisation technique we use is single crystal X-ray diffraction. This technique allows us to determine the chemical structure of reaction products. The CRL basement houses one Nonius Kappa-CCD and two Oxford Diffraction/Agilent SuperNovae single crystal diffractometers, which are all fitted with low temperature nitrogen cryostreams, allowing for the collection of data from air sensitive samples at a range of temperatures.

Single Crystal X-Ray Diffraction

Powder X-ray diffraction is frequently used to confirm that bulk samples have the same structure as single crystals. The Department of Chemistry houses several powder X-ray instruments including a PANalytical Empyrean Diffractometer which is well suited for air sensitive samples which can be flame sealed under nitrogen in capillary tubes.

Powder X-Ray Diffraction

Mass spectrometry enables us to determine the molecular mass and isotope distribution patterns of metal clusters in solution. This is a very powerful tool as each cluster will have an accurately predictable pattern which acts as a fingerprint to confirm its presence in solution. The group predominantly uses negative and positive ion-mode electrospray mass spectrometry as a characterisation tool, employing one of the two instruments located on the first floor of the CRL.

Mass Spectrometry

Solid-state crystallographic data is frequently supported by solution techniques such as NMR and mass-spectrometry. On the 2nd floor of the CRL we have access to a fully automated Bruker Avance III HD nanobay 400 MHz spectrometer for the running of routine samples. In the basement, we have access to a Bruker Avance III 500 MHz spectrometer which can be used for less common NMR active nuclei such as 29Si and 119Sn or for more customised experiments such as DOSY. Finally, the department also has a submission service for running samples on a Bruker Avance 500 MHz spectrometer equipped with a 13C cryoprobe

Nuclear Magnetic Resonance

For the more difficult to dry, hygroscopic solvents we have access to solvent stills.

Solvent Distillation

The group has access to the Centre for Advanced Electron Spin Resonance (CAESR). This facility contains state-of-the-art CW and pulse EPR instruments operating at X-band (9.4 GHz), Q-band (34 GHz), and W-band (94 GHz).

EPR

Join the
Group

Applications to join our team are always extremely welcome. We are always excited to hear from talented and enthusiastic Part II, DPhil and postdoctoral candidates. Please contact Jose directly by phone or email if you would like further information.

Part II Studentships

Jose Goicoechea supervises four Part II students each year. These projects involve a wide range of topics and generally include the synthesis and characterisation of new inorganic compounds. Contact Jose by email to discuss available research areas.

D.Phil Studentships

Studentships are typically advertised on the departmental webpage. Applications from overseas PhD candidates are very welcome. These applicants generally need to secure scholarships to fund their studies in Oxford. Information on Graduate Admissions, Studentships and sources of funding can be found in the Oxford University Graduate Prospectus, which is on-line here.

Postdoctoral Fellowships

Funded vacancies for postdoctoral research fellows in the Goicoechea group are advertised through the departmental job advert page. The links below provide details of other potential sources of funding: