Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance upgrade on Thursday 4th of May 2017 from 8.00am to 9.00am (BST).

During this time our websites will be offline temporarily. If you have any questions please use the feedback button on this page. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 21, 2013
Previous Article Next Article

Comparative properties of coordinated H2 and H2S at a ruthenium(II) centre

Author affiliations

Abstract

Thermodynamic data for the reversible formation of cis-RuCl2(P–N)(PPh3)(η2-H2) (2a) from trans-RuCl2(P–N)(PPh3) in C6D6 are determined by variable temperature 31P{1H} and 1H NMR spectroscopy; P–N = o-diphenylphosphino-N,N′-dimethylaniline. Values of ΔH° = −26 ± 4 kJ mol−1, ΔS° = −40 ± 15 J mol−1 K−1, and ΔG° (at 25 °C) = −13.8 ± 0.2 kJ mol−1 are compared with recently reported data for the corresponding H2S adduct (4a), where the exothermicity is greater by ∼20 kJ mol−1, but this is counteracted by a more unfavourable entropy change, and overall the K and ΔG° values at 25 °C are close. For loss of H2 from 2a in the solid state, whose X-ray structure is presented, ΔH° is 50 ± 3 kJ mol−1 as measured by Differential Scanning Calorimetry. The pKa values of the coordinated H2 (∼11) and H2S (∼14) are estimated by reactions of 2a and 4a with proton sponge (1,8-bis(dimethylamino)naphthalene) in CD2Cl2 at 20 °C; the mono-hydrido and -mercapto products are identified in situ. A corresponding H2O adduct is not deprotonated under the same conditions. Related dihydrido, mercapto and hydroxy species are formed by in situ reactions of 1a with NaH, NaSH, and NaOH, respectively.

Graphical abstract: Comparative properties of coordinated H2 and H2S at a ruthenium(ii) centre

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 30 Jan 2013, accepted on 08 Mar 2013 and first published on 08 Mar 2013


Article type: Paper
DOI: 10.1039/C3DT50314C
Citation: Dalton Trans., 2013,42, 7614-7621
  •   Request permissions

    Comparative properties of coordinated H2 and H2S at a ruthenium(II) centre

    E. S. F. Ma, D. C. Mudalige, B. O. Patrick and B. R. James, Dalton Trans., 2013, 42, 7614
    DOI: 10.1039/C3DT50314C

Search articles by author