Sandro Gambarotta

Transition Metal Chemistry and Catalysis

 

Most significant research contributions

Our research activity is directed towards both catalysis and low-valent metals for molecular activation. In catalysis our interest started with a study in vanadium chemistry by using a ligand system which has received substantial attention in the literature for its role in sustaining exceptional catalytic activity with late metals. Besides finding another potent catalyst, our paper in vanadium chemistry was the first insight into the direct involvement of the ligand system in the organometallic chemistry of the metal center (J. Am. Chem. Soc. 1999, 121, 9318). In an attempt to generalize these unique findings we have also tested middle metals and found what seemingly is an endless variety of transformations (J. Am. Chem. Soc. 2002, 124, 12268). Last but not least we also find that the ability of this ligand to work as electron storage allows a curious ambiguity in the metal oxidation state, which positively affects both catalytic performances and molecular activation (J. Am. Chem. Soc. 2005, 127, 13019). It is just in the last few months that we have made what we are convinced to be a major breakthrough. By designing a new type of hemilabile catalytic system, we are in the fortunate position of being able of preparing families of single component catalysts of extremely high polymerization activity (Angew. Chem. Int. Ed. 2007, 46, 6119). Still focusing on processes forming C-C bond from ethylene, we have started a project aimed at understanding the selective oligomerization. In search for working hypothesis, our research has initially focused on studying established catalytic systems and has yielded important insights into the factors promoting activity and selectivity (J. Am. Chem. Soc. 2006, 128, 9238, Angew. Chem. Int. Ed. Engl. 2006, 45, 7050, Angew. Chem. Int. Ed. Engl. 2008 in press).

In a separate line of research we pursue our interest for understanding activation of dinitrogen. Our recent work in f-block elements chemistry has provided evidences for the cooperative interaction of one-electron reductants on the same dinitrogen substrate, a feature somehow related to the behavior of the Fe cofactor of nitrogenase. Instead, by using a multi-electron reductant such a uranium and transient low-valent thorium synthons we have obtained the sole existing examples of dinitrogen cleavage and partial hydrogenation promoted by a f-block element (Angew. Chem. Int. Ed. Engl. 2002, 41, 3433, Angew. Chem. Int. Ed. Engl. 2003, 42, 4958, cited by C&En, Angew. Chem. Int. Ed. Engl 2003, 42, 814. Cited by C&En).

Patents:

  • Sebastiano Licciulli, Indira Thapa, Khalid AlBahily, Ilia Korobkov, Sandro Gambarotta,* Robbert Duchateau, Reynald Chevalier, Katrin Schuhen. Oligomerization of olefins US FR 6592; EP-FR6592
  • Sebastiano Licciulli, Sandro Gambarotta, Robbert Duchateau Supporttation of oligomerization catalyst Dutch Polymer Institute Filing in progress
  • Sebastiano Licciulli, Indira Thapa, Khalid AlBahily, Ilia Korobkov, Sandro Gambarotta, Robbert Duchateau, Reynald Chevalier, Katrin Schuhen. Highly Active oligomerization catalytic system. Filing in progress.

Refereed journal publications :
 

  • 235 Di Zhu,a Indira Thapa,b Ilia Korobkov,b Sandro Gambarotta,*,b Peter H.M. Budzelaar*,a., p-Acceptor ligands and organic radical chemistry, Inorg. Chem. In press
  • 234. Khalid Albahily,a Valeria Fomitcheva, a Sandro Gambarotta*, Ilia Korobkov, Muralee Murugesu* and Serge I. Gorelskya,c,Preparation and Characterization of a Reduced Chromium Complex via Vinyl Oxidative Coupling: Formation of a Self-Activating Catalyst for Selective Ethylene Trimerization.,J. Am. Chem. Soc. in press
  • 233. Khalid Albahily,a Yacoob Shaikh, a Elena Sebastiao, a Sandro Gambarotta,a* Ilia Korobkovb and Serge I. Gorelskya, Vinyl Oxidative Coupling as a Synthetic Route to Catalytically Active Monovalent Chromium, J. Am. Chem. Soc. in press
  • 232. Sebastiano Licciulli, Khalid Albahily, Valeria Fomitcheva, Ilia Korobkov, Sandro Gambarotta Robbert Duchateau, The first Chromium Ethylidene as a Potent Catalyst for Selective Ethylene Trimerization., Angew Chem. Int. Ed. Engl. 2011, ASAP
  • 231. Sebastiano Licciulli, Indira Thapa, Khalid AlBahily, Ilia Korobkov, Sandro Gambarotta, Robbert Duchateau, Reynald Chevalier, Katrin Schuhen., Towards Selective Catalytic Ethylene Tetramerization., Angew Chem. Int. Ed. Engl. 2010, 49, 9225∗
  • 230. Indira Thapa, Sandro Gambarotta, Robbert Duchateau, Shaneesh Vadake Kulangara and Reynald Chevalier, Switchable Chromium (II) Complexes of a Chelating Amidophosphine (N-P) for Ethylene Selective and non-Selective Oligomerization., Organometallics 2010, 29, 4080
  • 229. Sougandi Ilango, Balamurugan Vidjayacoumar, Sandro Gambarotta, Samarium complexes of a s-/p-pyrrolide/arene based macrocyclic ligand., Dalton Trans 2010, 39, 6853
  • 228. Ilia Korobkov and Sandro Gambarotta, Ligand Metallation in the Reactivity of a Tetravalent Uranium Amide,Inorg. Chem. 2010, 49, 3409
  • 227. Ilia Korobkov and Sandro Gambarotta, Reducing the Irreducible: Preparation of a Rare Paramagnetic Thorium Species, Organometallics 2010, 29 692
  • 226. Ilia Korobkov and Sandro Gambarotta, Unusual reactivity of a Tm-pyrrolide/aluminate complex with a metallocene-type of structural motif., Organometallics 2009, 28, 5560
  • 225. Grigory B. Nikiforov, Indu Vidyaratne, Sandro Gambarotta, Ilia Korobkov., Titanium-Promoted Dinitrogen Cleavage Partial Hydrogenation and Silylation., Angew. Chem. Int. Ed. Engl. 2009, 48, 7415.
  • 224. Indu Vidyaratne, Grigory B. Nikiforov, Serge I. Gorelsky, Sandro Gambarotta, Robbert Duchateau, Ilia Korobkov, Isolation of a self-activating ethylene trimerization catalyst, Angew. Chem. Int. Ed. Engl. 2009, 48, 6552.
  • 223. Ilia Korobkov, Sandro Gambarotta, Aluminate Sm(II) and Sm(III) Aryloxides. Isolation of a Single-component Ethylene Polymerization Catalyst, Organometallics 2009, 28, 4009
  • 222. Ilia Korobkov, Serge Gorelsky, Sandro Gambarotta, Reduced uranium complexes: synthetic and DFT study on the role of p-ligation in the stabilization of uranium species in a formal low-valent state., J. Am. Chem. Soc. 2009, 131, 10406.
  • 221. Steven Horvath, Serge I. Gorelsky, Sandro Gambarotta, Ilia Korobkov , Breaking the 1.80 Å Barrier of the Cr-Cr Multiple Bond Between Cr(II) Atoms., Angew. Chem. Int. Ed. Engl. 2008, 47, 9937.
  • 220. Amir Jabri, Chris B. Mason, Yan Sim, Sandro Gambarotta, Tara J. Burchell, Robbert Duchateau., Isolation of Single-Component Trimerization and Polymerization Chromium Catalysts: the Role of the Metal Oxidation State, Angew. Chem. Int. Ed. Engl. 2008, 47, 9717 (cited on C&En)
  • 219. Khalid Albahily, Danya Al-Baldawi, Sandro Gambarotta, Robbert Duchateau, Ece Koç, Tara J. Burchell., Isolation of a Chromium-Hydride Single-Component Ethylene Polymerization Catalyst., Organometallics 2008, 27, 22.
  • 218. Khalid Albahily, Danya Al-Baldawi, Sandro Gambarotta, Robbert Duchateau, Ece Koç, Tara J. Burchell., Preparation and Characterization of a Switcheable Single-Component Chromium Trimerization Catalyst., Organometallics 2008, 27 , 5943
  • 217. Khalid Albahily, Ece Koç, Danya Al-Baldawi, Didier Savard, Sandro Gambarotta,* Tara J. Burchell, Robbert Duchateau., Chromium Catalysts Supported by a non-Innocent NPN Ligand which Switch Activity from non- Selective Ethylene Oligomerization to Trimerization and Polymerization: Isolation of the First Single-Component Chromium Polymerization Catalysts., Angew. Chem. Int. Ed. Engl. 2008, 47, 5816.
  • 216. Sougandi Ilango,a Balamurugan Vidjayacoumar,a Sandro Gambarotta,a* Serge I. Gorelskyb, Low-Valent Vanadium Complexes of a Pyrrolide-Based Ligand. Electronic Structure of a Dimeric V(I) complex with a Short and Weak Metal-Metal Bond., Inorg. Chem. 2008, 47, 3265
  • 215. Indu Vidyaratne, Jennifer Scott, Sandro Gambarotta, Peter Budzelaar, Multiple pathways of dinitrogen activation during the reduction of a Fe bis-imino pyridine complex, Inorg. Chem. 2008, 47, 896 (most accessed article Jan-Apr 2008).
  • 214. Indu Vidyaratne, Patrick Crewdson, Emeric Lefebvre, Sandro Gambarotta, Dinitrogen Coordination and Cleavage Promoted by a Vanadium Complex of a s,p,s - Donor Ligand., Inorg. Chem. 2007, 46, 8836.
  • 213. P.G. Cozzi, S. Gambarotta, M. Monatri, L. Zoli, Convenient preparation of chiral dipyrrolyl methanes., Collect. Czech. Chem. Commun. 2007, 72, 1046 (invited) .
  • 212. Indu Vidyaratne, Jennifer Scott, Sandro Gambarotta, Peter Budzelaar, Dinitrogen fixation, partial reduction and formation of coordinated imide promoted by a chromium bis-iminopyridine complex., Inorg. Chem. 2007, 46, 7040
  • 211. Claire N. Temple, Sandro Gambarotta, Ilia Korobkov, Robbert Duchateau, New Insight into the Role of the Metal Oxidation State in Controlling the Selectivity of the Cr-(SNS) Ethylene Trimerization Catalyst , Organometallics 2007, 26, 4598
  • 210. Amir Jabri, Ilia Korobkov, Sandro Gambarotta, Robbert Duchateau, Single-site, single-component catalysts for very high Mw polyethylene: a robust “ready-to-go” vanadium p-bonded complex without a pre-formed V-C bond., Angew. Chem. Int. Ed. 2007, 46, 6119.
  • 209. Indu Vidyaratne, Jennifer Scott, Sandro Gambarotta and Robbert Duchateau, The reactivity of chromium complexes of a bis-iminopyridine ligand: highly active ethylene polymerization catalysts carrying the metal in a formally low oxidation state., Organometallics 2007, 26, 3201.
  • 208. Grigory B. Nikiforov, Patrick Crewdson, Sandro Gambarotta*, Ilia Korobkov and Peter, H. M. Budzelaar*, Reduction of Titanium supported by a s-/p-bonded Tripyrrole Ligand: Ligand C-N Bond Cleavage and Coordination of Olefin and Arene with an inverse Sandwich Structure., Organometallics 2007, 26, 48
  • 207. Knijnenburg, Q.; Gambarotta, S.; Budzelaar, P.H.M. , Ligand-centred reactivity in diiminepyridine complexes , Dalton Trans. 2006, 5442 .
  • 206. Claire Temple, Amir Jabri, Pat Crewdson, Sandro Gambarotta, Ilia Korobkov, The Question of the Cr Oxidation State in the (SNS)Cr [(SNS) = CySCH2CH2N(H)CH2CH2SCy] Catalyst for Selective Ethylene Trimerization: An Unanticipated Re-oxidation Pathway., Angew. Chem. Int. Ed. Engl. 2006, 45, 7050
  • 205. Harminder Phull, Davide Alberti, Ilia Korobkov, Sandro Gambarotta, Fixation of CO2 by magnesium cations: a re-interpretation, Angew. Chem. Int. Ed. Engl. (HOT papers section) 2006, 45, 5331
  • 204. Athimoolam Arunachalampillai, Patrick Crewdson, Ilia Korobkov and Sandro Gambarotta, Ring opening, C-O and C-N bond cleavage by transient reduced Th species., Organometallics, 2006, 25, 3856
  • 203. Amir Jabri, Claire Temple, Patrick Crewdson, Sandro Gambarotta, Ilia Korobkov, Robbert Duchateau, Role of the metal oxidation state in the SNS-Cr catalyst for ethylene trimerization. Isolation of di- and trivalent cationic intermediates. , J. Am. Chem. Soc. 2006, 128, 9238
  • 202. Amir Jabri, Patrick Crewdson, Sandro Gambarotta, Ilia Korobkov, Isolation of a cationic Cr(II) species in a catalytic system for ethylene tri- and tetramerization, Organometallics 2006, 25, 715
  • 201. Jennifer Scott, Sandro Gambarotta, Ilia Korobkov and Peter Budzelaar, Reduction of bis-iminopyridineFe: evidence for a non-cationic polymerization pathway?, Organometallics 2005, 24, 6298.
  • 200. Jennifer Scott, Sandro Gambarotta,* Ilia Korobkov, Q. Knijnenburg, Bas de Bruin and Peter Budzelaar, Formation of a paramagnetic Al complex and extrusion of Fe during the reaction of (diiminepyridine)Fe with AlR3 (R = Me, Et)., J. Am. Chem. Soc. 2005, 127, 17204.
  • 199. Patrick Crewdson, Sandro Gambarotta, Marie-Charlotte Djoman, Ilia Korobkov, Robbert Duchateau, Switchable Cr(II) Ethylene Oligomerization/Polymerization Catalyst, Organometallics 2005, 24, 5214.
  • 198. Jennifer Scott, Sandro Gambarotta, Ilia Korobkov and Peter H.M. Budzelaar, Metal versus ligand alkylation in the reactivity of the (bis-iminopyridinato)Fe catalyst, J. Am. Chem. Soc. 2005, 127, 13019.
  • 197. Arunachalampillai Athimoolam, Sandro Gambarotta* and Ilia Korobkov, Preparation, Characterization and Structure of two Dipyrrolide Thorium Homoleptic Complexes: Isolation of a Dipyrrolide Dipotassium Salt with an Inverted-Sandwich Type of Structure., Can. J. Chem. (special issue dedicated to H. Alper) 2005, 83, 832.
  • 196. Arunachalampillai Athimoolam, Sandro Gambarotta and Ilia Korobkov, Ligand metallation during the reduction of a Th(IV) amide complex, Organometallics 2005, 24, 1996.
  • 195. Indu Vidyaratne , Sandro Gambarotta , Ilia Korobkov , Peter H. M. Budzelaar , Dinitrogen Partial Reduction by Formally Zero- and Divalent Vanadium Complexes Supported by the Bis-iminopyridine System, Inorganic Chemistry 2005, 44, 1187
  • 194. J. Scott, S. Gambarotta, I. Korobkov, Ligand-assisted reduction of Co(II) to Co(I) and subsequent fixation of dinitrogen
  • Can. J. Chem. (special issue dedicated to N2 fixation) 2005, 83, 279.
  • 193 S. Gambarotta, I. Korobkov, Trivalent Uranium, Progress in Inorg. Chem. 2005, 54, ch-4
  • 192 Ilia Korobkov, Athimoolan Arunachalampillai and Sandro Gambarotta, Cyclometallation and solvent deoxygenation during reduction of a homoleptic Th(OAr)4 complex: serendipitous formation of a terminally bonded Th-OH function., Organometallics 2004, 23, 6248.
  • 191 S. Gambarotta, I. Korobkov, cis- Double Addition of CO2 to a Coordinated Arene of a Thorium Complex., Organometallics 2004, 23, 5379
  • 190. H. Sugiyama, S. Gambarotta, G. P. A. Yap, D. R. Wilson, S. K.-H. Thiele, Preparation of an active Nd catalyst for regioselective butadiene cis-polymerization supported by a dianionic modification of the 2,6-diiminopyridine ligand, Organometallics 2004, 23, 5054
  • 189. Hiroyasu Sugiyama, Ilia Korobkov, Sandro Gambarotta, Angela Möller, Peter H.M. Budzelaar, Preparation, characterization and magnetic behavior of the Ln derivatives (Ln = Nd, La) of a 2,6-diiminepyridine ligand and corresponding di-anion. , Inorg. Chem. 2004, 43, 5771
  • 188. H. Gao, I. Korobkov, S. Gambarotta, Divalent molybdenum complexes of the dipyrrolide ligand system. Isolation of a Mo2 unit with a 45° twist angle., Inorg. Chem. 2004, 43, 1108
  • 187 Jennifer Scott, Sandro Gambarotta, Multimetallic cooperative activation of N2, Angew. Chem. Int. Ed. Engl. 2004, 43, 5298, Angew. Chem. Int. Ed. Engl. (V.I.P. section) 2003 42, 4958 Cited by C&En
  • 184. Christian D. Bérubé, Sandro Gambarotta, Glenn P. A. Yap, Serendipitous isolation of the first example of a mixed-valence samarium tripyrrane complex, Organometallics 2003, 22, 3742.
  • 181. Ilia Korobkov, Sandro Gambarotta, Glenn P. A. Yap, The first thorium arene complex: a divalent synthon, Angew. Chem. Int. Ed. Engl 2003, 42, 814. Cited by C&En
     

Chapters in Encyclopedia:
 

  • 1. P.Berno, D. Richeson, S.Gambarotta - Vanadium Comprehensive Organometallic Chemistry. II Edition 1982-1992 G. Wilkinson Ed, Pergamon Press, Oxford in press.
  • 2. J. Jubb, D.Richeson, J. Song, S. Gambarotta - Zirconium and Hafnium. Comprehensive Organometallic Chemistry. II Edition 1982-1992. G. Wilkinson Ed, Pergamon Press, Oxford in press.

Recent Invited Lectures at International Conferences and Symposia (2004-2007)

  • 48 CIC Hamilton 2009-11-26
  • 50. Asian Polyolefin Organization Seoul 2009.
  • 51 University of Canberra, Sydney, Melbourne, and Tasmania 2009 (2 lectures)
  • 52. SK-Energy, Daejeon 2009
  • 53 Chungnam Natl. Univ in Daejeon, Korea. 2009
  • 54 Kyung Hee Univ Seoul, 2009
  • 55 Korean chemical society meeting in Daejeon 2009.
  • 56. Korea Univ. 2009
  • 57 CIC Tororonto 2010
  • 58 Dow Chemical Midland (MI) 2010
  • 59 Key Note Lectures Blue Ski conference Sorrento 2010

ACS Philadelphia Aug 2008; ISHC Florence July 2008; Lectures at University of Erlangen, Bayereuth, Regensburg, Wurzburg, June 2008; OZOM Camberra January 2008; Basell Frankfurt 2006; ACS (San Francisco) Sept 2006; Catalysis Symposium University of Florida April 2006; Am2Net Munster 2004; ASm2Net Calgary 2005; Pacifichem 2005 (2 lectures); Rare Earth Conference Bayereuth 2004.

Honorary Memberships, Lectureships and Awards

  • Member of the Editorial Board of J. of Organometallic Chemistry (1994-1998); Alcan Lecture Award 1996; Fellow of the Chemical Institute of Canada; NSERC GSC (Committee 24, 2001-2004).
  • Member of the Editorial Board of Organometallics (2003-2006); 2002 Gerhard Scholss Lecturer, University of Chicago.