Decaborane Thiols as Building Blocks for Self-Assembled Monolayers on Metal Surfaces

0377295 - ÚACH 2013 RIV US eng J - Článek v odborném periodiku
Bould, Jonathan - Macháček, Jan - Londesborough, Michael Geoffrey Stephen - Macias, R. - Kennedy, D. J. - Bastl, Zdeněk - Rupper, P. - Baše, Tomáš
Decaborane Thiols as Building Blocks for Self-Assembled Monolayers on Metal Surfaces.
Inorganic Chemistry. Roč. 51, č. 3 (2012), s. 1685-1694. ISSN 0020-1669. E-ISSN 1520-510X
Grant CEP: GA AV ČR(CZ) KAN400480701; GA AV ČR KAN100400702; GA AV ČR(CZ) IAA400320901; GA ČR(CZ) GAP207/11/1577; GA ČR GAP205/10/0348
Klíčová slova: metallaborane reaction chemistry * containing cluster chemistry * reversible capture
Kód oboru RIV: CA - Anorganická chemie
Impakt faktor: 4.593, rok: 2012

Three nido-decaborane thiol cluster compounds, [1-(HS)-nido-B10H13] 1, [2-(HS)-nido-B10H13] 2, and [1,2-(HS)(2)-nido-B10H12] 3 have been characterized using NMR spectroscopy, single-crystal X-ray diffraction analysis, and quantum-chemical calculations. In the solid state, 1, 2, and 3 feature weak intermolecular hydrogen bonding between the sulfur atom and the relatively positive bridging hydrogen atoms on the open face of an adjacent cluster. Density functional theory (DFT) calculations show that the value of the interaction energy is approximately proportional to the number of hydrogen atoms involved in the interaction and that these values are consistent with a related bridging-hydrogen atom interaction calculated for a B18H22 center dot C6H6 solvate. Self-assembled monolayers (SAMs) of 1, 2, and 3 on gold and silver surfaces have been prepared and characterized using X-ray photoelectron spectroscopy. The variations in the measured sulfur binding energies, as thiolates on the surface, correlate with the (CC2) calculated atomic charge for the relevant boron vertices and for the associated sulfur substituents for the parent B10H13(SH) compounds. The calculated charges also correlate with the measured and DFT-calculated thiol H-1 chemical shifts. Wetting-angle measurements indicate that the hydrophilic open face of the cluster is directed upward from the substrate surface, allowing the bridging hydrogen atoms to exhibit a similar reactivity to that of the bulk compound. Thus, [PtMe2(PMe2Ph)(2)] reacts with the exposed and acidic B-H-B bridging hydrogen atoms of a SAM of 1 on a gold substrate, affording the addition of the metal moiety to the cluster. The use of reactive boron hydride SAMs as templates on which further chemistry may be carried out is unprecedented, and the principle may be extended to other binary boron hydride clusters.
Trvalý link: http://hdl.handle.net/11104/0006995