Issue 5, 1996

Multinuclear solid-state nuclear magnetic resonance studies on transition-metal clusters containing hydrides

Abstract

Solid-state 1H and D NMR measurements have been made for all transition-metal carbonyl clusters containing interstitial hydrides/deuterides previously characterised by neutron diffraction. There is a close agreement between the values of δ(1H/D) in solution and the solid state except for [Co6H(CO)15]. The values of δ(1H) for interstitial hydrides are in the range δ+ 18.5 to –26.8; the shift to high field is shown to be due to an increasing displacement of H from the centre of the metal octahedral cavity, consistent with surface tensor harmonic theory. Whereas migration of H readily occurs in both [Rh13Hx(CO)24](5–x)–(x= 2 or 3) and [Ru2Rh2H2(CO)12] in solution, solid-state 1H NMR measurements on [Rh13Hx,(CO)24](5–x)–(x= 2 or 3) showed that there is no evidence for such migration in the solid state and for [Ru2Rh2H2(CO)12] oscillation of H about the metal–metal edge(s) occurs rather than migration to different edges as found in solution.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1996, 625-630

Multinuclear solid-state nuclear magnetic resonance studies on transition-metal clusters containing hydrides

T. Eguchi, B. T. Heaton, R. Harding, K. Miyagi, G. Longoni, J. Nähring, N. Nakamura, H. Nakayama, T. A. Pakkanen, J. Pursiainen and A. K. Smith, J. Chem. Soc., Dalton Trans., 1996, 625 DOI: 10.1039/DT9960000625

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