PN-III-P4-ID-PCE-2016-0089

 

 

Molecular metal clusters: bridging the gap between small molecules and nanocrystals

 

Metal clusters have received increasing attention in the recent years owing to their unique properties that bridge a gap between small molecules and nanocrystals, as well as potential applications in numerous areas including catalysis, biomedicine, electronic and optical materials. Transition metals are capable of exhibiting high coordination numbers and do not necessarily obey the classical electron counting rules. The proposed research uses density functional theory methods to explore structure, bonding, thermochemistry, and chemical reactivity of various metal clusters. Such systems often exhibit unprecedented structures based on unusual polyhedra not otherwise found in chemistry. Our research project is concentrated in six areas: cyclopentadienylmetal clusters of the transition metals, incorporation of interstitial atoms in transition metal clusters, coinage metal clusters with external chelating sulfur ligands, assessment of the effect of substituting coinage metal atoms such as gold and silver with various main group heteroatoms, and evaluation the systematics of organogallium and organoindium clusters.

 

The list of people involved in this project

 

Nr.

Surname and name

Position

1.

Alexandru Lupan

Project director

2.

Amr Attia

Researcher

3.

Attila-Zsolt Kun

Researcher

4.

Matei-Maria Uţă

Researcher

5.

Boboș Liviu Dorel

Researcher

6.

Pușcaș Cristina Maria

Researcher

7.

Adrian Brânzanic

PhD student

8.

Noemi Deak

PhD student

9.

Luana-Flavia Radu

PhD student

10.

Szabolcs Jako

MSc student

 

 

Results

 

Publications

1. "Reversible complexation of ammonia by breaking a manganese-manganese bond in a manganese carbonyl ethylenedithiolate complex: A theoretical study of an unusual type of Lewis acid" L.F. Radu, A.A. Attia, R. Silaghi-Dumitrescu, A. Lupan, R.B. King, Dalton Trans., 2019, 48, 324-332; doi: 10.1039/C8DT04217A

2. "Spherical closo deltahedra with surface metal-metal multiple bonding versus oblate deltahedra with internal metal-metal bonding in dichromadicarbaborane structures: the nature of Stone’s icosahedral dichromadicarbaborane" S. Jako, A. Lupan, A.Z. Kun, R.B. King, Inorg. Chem., 2019, 58, 3825-3837; doi: 10.1021/acs.inorgchem.8b03476

3. "The isocloso capped pentagonal bipyramid versus the closo bisdisphenoid in hypoelectronic eight-vertex metallaboranes having 16 skeletal electron" R.A. Șeptelean, A.A. Attia, A. Lupan, R.B. King, Int. J. Quant. Chem., 2019, 119, e25880; doi: 10.1002/qua.25880

4. "Segregation of tetracarbon units in low-energy tetracarbindane structures: major differences from their aluminum and gallium analogues" A.A. Attia, A. Lupan, R.B. King, Int. J. Quant. Chem., 2019, 119, e25934; doi: 10.1002/qua.25934

5. "Binuclear pentalene titanium carbonyls: comparison with related cyclopentadienyltitanium carbonyls" L.F. Radu, A.A. Attia, A. Lupan, R.B. King, Int. J. Quant. Chem., 2018, 118, e25762; doi: 10.1002/qua.25762

6. "Opening cobaltadicarbaborane deltahedra by external dimethylamino substituents: conversion of icosahedra to isonido 12-vertex polyhedra" A.A. Attia, A. Lupan, R.B. King, Polyhedron, 2018, 151, 458-464; doi: 10.1016/j.poly.2018.06.003

7. "Binuclear pentalene titanium carbonyls involved in the deoxygenation of carbon dioxide" L.F. Radu, A.A. Attia, A. Lupan, R.B. King, J. Organomet. Chem., 2018, 867, 201-207; doi: 10.1016/j.jorganchem.2017.11.006

8. "Tetracapped tetrahedral ruthenium-sulfur clusters related to iron-sulfur structural units in metalloenzymes"  A. Lupan, R. Silaghi-Dumitrescu, R.B. King, Inorg. Chim. Acta., 2018, 475, 193-199; doi:10.1016/j.ica.2017.10.011

9. "Major differences between preferred tetracarbagallane and tetracarbalane structures" A.A. Attia, A. Lupan, R.B. King, J. Organomet. Chem., 2018, 864, 88-96; doi: 10.1016/j.jorganchem.2018.01.051

10. "Polyhedral trimetallaboranes of the group 9 metals: isocloso versus capped and uncapped closo deltahedra" A.A. Attia, A. Lupan, R.B. King, Organometallics, 2018, 37, 1845-1851; doi: 10.1021/acs.organomet.8b00077

11. "New class of hybrid materials for detection, capture and on-demand release of carbon monoxide" A. Pitto-Barry, A. Lupan, C. Ellingford, A.A. Attia, N.P. Barry, ACS Appl. Mater. Interfaces, 2018, 10, 13693-13701; doi: 10.1021/acsami.8b01776

12. "The high affinity of small-molecule antioxidants for hemoglobin" C. Puscas, L. Radu, F. Carrsascoza, A.C. Mot et.al, Free Radic. Biol. Med., 2018, 124, 260-274; doi: 10.1016/j.freeradbiomed.2018.06.019

13. "Heme Fe-SO2− intermediates in sulfite reduction: Contrasts with Fe-OO2− species from oxygen–oxygen bond activating systems" M. Surducan, A. Branzanic, R. Silaghi-Dumitrescu, Int. J. Quant. Chem., 2018, 118, e25697; doi: 10.1002/qua.25697

14. "Group 9 metallatelluraboranes: comparison with their sulfur analogues" A.A. Attia, A. Lupan, R.B. King, J. Organomet. Chem., 2018, 865, 145-151; doi: 10.1016/j.jorganchem.2018.01.058

15. "Aluminum-poor hexacarbalane structures: the transition from localized organoaluminum structures to delocalized polyhedra" A.A. Attia, A. Lupan, R.B. King, Int. J. Quant. Chem., 2018, 118, e25506; doi: 10.1002/qua.25506

 

Conferences

1. "Paramagnetism and metal-metal bonding in metallaboranes" oral presentation by A. Lupan at the 8th European Conference on Boron Chemistry, 24 - 27 June 2018, Montpellier, France

2. "Rhenatricarbaboranes Having 2n + 2 Wadean Skeletal Electrons: Closo vs. Isocloso deltahedra " poster presentation by A. Attia at the 8th European Conference on Boron Chemistry, 24 - 27 June 2018, Montpellier, France

3. "Unusual polyhedra in organoaluminum carbon clusters: a theoretical view" invited lecture by A. Lupan at the 28th International Conference on Organometallic Chemistry, 15 - 20 July 2018, Florence, Italy

4. "Heme vs. siroheme models of the sulfite reductase active site" oral presentation by A. Branzanic at the XI All-Russian School-Conference of Young Scientists - Theoretical and experimental chemistry of liquid-phase systems, 30 October - 4 November 2017, Ivanovo, Russia