Polyhedral metallaboranes: metal clusters stabilized in borane matrices


Incorporating transition metals into a borane cage creates novel metal environments that modify their reactivity and hence their catalytic properties. Molecules based on such systems have potential applications in homogenous catalysis. Related metallaboranes with metal carbonyl vertices are potentially useful as precursors for the preparation of special metal boride materials with novel electronic, magnetic, and optical properties. Our recent studies have focused on such systems, with theoretical predictions that agree well with experimental data on numerous derivatives – thus confirming the reliability of our methods. The general objective of this research project is understanding the structure, bonding, thermochemistry, and chemical reactivity of polyhedral metallaboranes, particularly those containing two or more transition metal vertices. To this end, density functional theory methods will be employed on various families of transition metal boranes. The research will focus on the study of internal and surface metal-metal bonding in dimetallaborane clusters of Ni and Mn, as well as on recently-reported hydrogen-rich oblatonido species having more open polyhedral structures, borane iron carbonyl derivatives, metallathiaboranes, trimetallaboranes and supraicosahedral systems. The influence of external factors, from solvation to interaction with biological ligands, including metallaborane-protein binding of potential medical importance, will also be examined.


The list of people involved in this project



Surname and name



Alexandru Lupan

Project director


Amr Attia



Attila-Zsolt Kun



Raluca Şeptelean



Matei-Maria Uţă



Adrian Brânzanic

PhD student


Noemi Deak

PhD student


Luana-Flavia Radu

PhD student


Szabolcs Jako

BSc student






1. "Nonspherical Deltahedra in Low-Energy Dicarbalane Structures Testing the Wade–Mingos Rules: The Regular Icosahedron Is Not Favored for the 12-Vertex Dicarbalane"  A. Attia, A. Lupan, R.B. King, Inorg. Chem., 2015, 10.1021/acs.inorgchem.5b02014

2. "Unusual dimetallaborane cluster polyhedra and their skeletal bonding" A. Lupan, A.A. Attia, R.B. King, Coord. Chem. Rev., in press; doi: 10.1016/j.ccr.2016.11.001

3. "Hypoelectronicity and Chirality in Dimetallaboranes of the Group 9 Metals Cobalt, Rhodium, and Iridium" S. Jákó, A. Lupan, A.Z. Kun, R.B. King, Inorg Chem, accepted

4. "Tetracarbaboranes: nido structures without bridging hydrogens" A.A. Attia, A. Lupan, R.B. King, Dalton Trans., in press; doi: 10.1039/C6DT03507H

5. "Hydrogen migration in hypoelectronic biicosahedral metallaborane structures" A.A. Attia, A. Lupan, R.B. King, RSC Adv., 2016, 6, 87096-87102; doi: 10.1039/C6RA16304A

6. "Tetracarbalane structures: nido polyhedra and non-spherical deltahedra" A.A. Attia, A. Lupan, R.B. King, Dalton Trans., 2016, 45, 11528-11539; doi: 10.1039/c6dt01982j

7. "Dimetallaborane analogues of the octaboranes of the type Cp2M2B6H10: structural variations with changes in the skeletal electron count" A.M.V. Brânzanic, A. Lupan, R.B. King, Dalton Trans., 2016, 45, 9354-9362; doi: 10.1039/C6DT00985A

8. "Novel Non-spherical Deltahedra in Trirhenaborane Structures" A.A. Attia, A. Lupan, R.B. King, New J. Chem., 2016, 40, 7564-7572; doi:10.1039/c6nj01922f

9. "Pairing of carbon atoms in low-energy deltahedral dicarbagallane structures derived from vertex expansion of closo deltahedra" A.A. Attia, A. Lupan, R.B. King, J. Organometal. Chem., 2016, 819, 173-181; doi: 10.1016/j.jorganchem.2016.06.034

10. "Sulfur and carbon as heteroatoms in ferrathiacarboranes" A.A. Attia, A. Lupan, R.B. King, Polyhedron, 2016, 113, 109-114; doi:10.1016/j.poly.2016.04.027

11. "Polyhedral cobaltadiselenaboranes: nido structures without bridging hydrogen atoms" A.A. Attia, A. Lupan, R.B. King, RSC Adv., 2016, 6, 53635-53642; doi: 10.1039/C6RA09821E

12. "Polyhedral dinickelaboranes as analogues of the dicarbaboranes" S. Jákó, A. Lupan, A.Z. Kun, R.B. King, Polyhedron, 2016, 110, 31-36; doi: 10.1016/j.poly.2016.02.016

13. "Contrasting behavior of the group 15 elements (P, As, Sb, Bi) as heteroatoms in icosahedral cobaltaboranes: effect of phosphorus atom basicity " A.A. Attia, A. Lupan, R.B. King, Rev. Roum. Chim, 2016, 61, 247-250; WOS:000385693200005

14. "Biicosahedral metallaboranes: aromaticity in metal derivatives of three-dimensional analogues of naphthalene" A.A. Attia, A. Lupan, R.B. King, Phys. Chem. Chem. Phys., 2016, 18, 11707-11710; doi: 10.1039/c5cp05708f

15. "Cyclopentadienylironphosphacarboranes: fragility of polyhedral edges in the 11-vertex system" A.A. Attia, A. Lupan, R.B. King, RSC Adv., 2016, 6, 1122-1128; doi: 10.1039/10.1039/C5RA17070B



1. YYRICCCE I - Young Researchers' International Conference on Chemistry and Chemical Engineering, 12 - 15 May 2016, Cluj-Napoca, Romania, oral presentation by A. Lupan, "Metallaboranes containing main group heteroatoms"

2. ClusPom Conference (Clusters and Polyoxometalates), 29 June - 2 July 2016, Rennes, France, oral presentation by A. Lupan, "Mixed aluminum-carbon clusters in organoaluminum chemistry"

3. ICCC - International Conference on Coordination Chemistry, 3 - 8 July 2016, Brest, France, poster presentation by A. Lupan, "Group 15 elements as vertex atoms in metallaboranes"

4. ICOMC - International Conference on Organometallic Chemistry, 17 - 22, July 2016, Melbourne, Australia, oral presentation by A. Lupan, "Polyhedral metallaboranes with group 15 heteroatoms"

5. SfS Chemistry - International Conference Students for Students, 13 - 17, April 2016, Cluj-Napoca, Romania, oral presentation by S. Jako, "Dimetallaboranes of the First Row Transition Metals: Nickel and Cobalt Derivatives"

6. Würzburg Summer School 2016 on Molecular Boron Chemistry, 25-29 July, 2016, Wurzburg, Germany, poster presentation by A. Branzanic "Theoretical investigation of 5-vertex hydrogen-rich dimetallaboranes of 2nd and 3rd row transition metals"