Treatment of CpRuH(dppm) (dppm = 1,1-bis(diphenylphosphino)methane) and CpRuH(dppe) (dppe = 1,2-bis(diphenylphosphino)ethane) with TIPF₆ in THF produced η²-(H-Tl) complexes [CpRu(dppm)(η²-(H-Tl))]PF₆ (II-2) and [CpRu(dppe)(η²-{H-Tl(THF)})]PF₆ (II-4), respectively. Complexes II-2 and II-4 are the first structurally characterized η²-hydride complexes of period 6 main group elements.

Treatment of RuCl₂(PPh₃)₃ with 6-dimethylaminopentafulvene (III-4) in THF in the presence of water produced (η⁵-C₅H₄CHO)RuCl(PPh₃)₂ (III-6), which reacted with NaBH₄ to give the Ru-H···HO dihydrogen bonded complex (η⁵-C₅H₄CH₂OH)RuH(PPh₃)₂ (III-7). The dihydrogen bonded complex (η⁵-C₅H₄CH₂OH)RuH(PPh₃)₂ (III-7) could also be obtained by the reaction of NaBH₄ with the complex (η⁵-C₅H₄CHO)RuH(PPh₃)₂ (III-9), whi...[ Read more ]

Treatment of CpRuH(dppm) (dppm = 1,1-bis(diphenylphosphino)methane) and CpRuH(dppe) (dppe = 1,2-bis(diphenylphosphino)ethane) with TIPF₆ in THF produced η²-(H-Tl) complexes [CpRu(dppm)(η²-(H-Tl))]PF₆ (II-2) and [CpRu(dppe)(η²-{H-Tl(THF)})]PF₆ (II-4), respectively. Complexes II-2 and II-4 are the first structurally characterized η²-hydride complexes of period 6 main group elements.

Treatment of RuCl₂(PPh₃)₃ with 6-dimethylaminopentafulvene (III-4) in THF in the presence of water produced (η⁵-C₅H₄CHO)RuCl(PPh₃)₂ (III-6), which reacted with NaBH₄ to give the Ru-H···HO dihydrogen bonded complex (η⁵-C₅H₄CH₂OH)RuH(PPh₃)₂ (III-7). The dihydrogen bonded complex (η⁵-C₅H₄CH₂OH)RuH(PPh₃)₂ (III-7) could also be obtained by the reaction of NaBH₄ with the complex (η⁵-C₅H₄CHO)RuH(PPh₃)₂ (III-9), which was in turn obtained by the reaction of RuHCl(PPh₃)₃ with 6-dimethylaminopentafulvene (III-4) in the presence of water. The analogous dihydrogen bonded osmium complex (η⁵-C₅H₄CH₂OH)OsH(PPh₃)₂ (III-12) was similarly prepared. Single crystal structures of III-7 and III-12, and DFT calculations support the presence of intra-molecular H···H separatied around 1.9 to 2.0 Å.

Reaction of the diazocyclopentadiene phosphazine C₅H₄N₂PPh₃ with (p-cymene)RuCl₂(PPh₃) or RuCl₂(PPh₃)₃ produced half-sandwich (η⁵-C₅H₄Cl)RuCl(PPh₃)₂ (IV-3). Similarly, ( η⁵-C₅H₄R)OsCl(PPh₃)₂ (IV-6) was obtained from the reaction of C₅H₄N₂PPh₃ with OsCl₂(PPh₃)₃. Complexes ( η⁵-C₅H₄Cl)Ru(p-cymene)(BPh₄) (IV-4) and (η⁵-C₅H₄Cl)Os(p-cymene)(BPh₄) (IV-5) with sandwich structures were isolated from reaction of C₅H₄N₂PPh₃ with (p-cymene)RuCl₂(PPh₃) and (p-cymene)OsCl₂(PPh₃) with addition of NsBPh₄, respectively.

A convenient method for regioselective H/D exchange reactions between D₂O and alcohols at both α- and β-carbon positions using RuCl₂(2-NH₂CH₂Py)(PPh₃)₂ (2-NH₂CH₂Py = 2-aminomethylpyridine)/KOH was developed. With the study of catalytic properties of a series of ruthenium complexes for H/D exchange between D₂O and alcohols, the catalytic activity of the ruthenium complexes and regioselectivity of the H/D exchange reactions were found to be dependent on the auxiliary ligands. The H/D exchange reactions proceed through an oxidation/modification/reduction reaction sequence involving hydride species. The different regioselectivities of the H/D exchange reactions catalyzed by these ruthenium complexes can be related to the relative easiness of exchange reactions of ruthenium hydride intermediates with D₂O.

The catalytic properties of a series of ruthenium complexes for β-alkylation of secondary alcohols with primary alcohols were studied. The system RuCl₂(2-NH₂CH₂Py)(PPh₃)₂ (2-NH₂CH₂Py = 2-aminomethylpyridine)/KO^tBu was found to be efficient for β-alkylation of secondary alcohols with primary alcohols.