Ionic ruthenium(IV) trihydrides as intermediates in the heterolytic fission of dihydrogen by five-co-ordinate hydridoruthenium(II) cations. Direct evidence for an oxidative addition–reductive elimination pathway

(η5-C5H5)Ru(PPh3)H3: a stable ruthenium (IV) trihydride

“…In contrast to the reaction of (2) and consistent with the mechanism in Scheme 1, the reaction of (q5-C5H5)Ru(Ph,PCH2-CH,PPh2)Cl (4) ), 2.0 (m, CH2), -12.9 (t, J 34 Hz, RuH)]. Phosphine loss from the bidentate system is disfavoured and so a pathway leading to a ruthenium(rv) trihydride cannot be followed in this case.…”

The hydride route to the preparation of dinitrogen complexes

“…[57][58][59][60][61][62] NMR data also suggested intramolecular exchange of H atoms between the terminal hydride and the dihydrogen ligand in the iron and osmium complexes, 61 contrasting with the ruthenium analogue that presents a more labile ligand. 63,64 Of all the compounds of the type [(R 2 PCH 2 CH 2 PR 2 ) 2 MH(H 2 )] + , only the iron complexes are nitrogen sensitive as dihydrogen is rapidly replaced by N 2 generating 23 (Scheme 5). The difference in reactivity between Fe and Os complexes could be explained by the strong interactions of the hydride and dihydrogen ligands with osmium.…”

Dihydrogen complexes as prototypes for the coordination chemistry of saturated molecules

“…It would take more than a year before others were identified, notably by Morris, Crabtree, Chaudret, and Heinekey. This quartet has since performed elegant synthetic, reactivity, and NMR studies on H 2 and silane complexes (5,(25)(26)(27)(28)(29)(30) (33). However, attempts to prove H 2 binding here was problematic, even long after H 2 binding was established (34).…”