Cyclopentadienyl-ruthenium and -osmium chemistry. XXIII. Synthesis and reactions of some hydrido complexes containing ruthenium or osmium, and related chemistry

Abstract

The hydrido complexes HM(PPh3)2(η-C5H5) (M = Ru, Os), HFe(dppe)(η-C5H5), HRu(L2)(η-C5H5) (L2 = dppe, dppm or dpae), HRu(AsPh3),(η-C5H5), HRu(L)(PPh3)(η-C5H5) [L = CNBut, P(OPh)3] have been obtained from reactions between the analogous chloro complexes and NaOMe/MeOH; RuCI[P(OPh)3]2(η-C5H5) affords the cyclometallated Ru[(C6H4O)P(OPh)3)2][P(Oph)3]η-C5H5) under these conditions. Reactions between HRu(PPh3)2(η C5H5) and HX or CHX3 (X = Cl, Br, I) afford the corresponding halo complexes RuX(PPh3)2(η-C5H5); CS2 reacts with HRuL2(η-C5H5) (L = PPh3, L2 = dppe) to give the corresponding dithioformato derivatives. Ligand-exchange reactions of HRu(PPh3)2(η -C5H5) with CO or dppe proceed with difficulty at temperatures of c. 150-200�C in an autoclave.

(Alkenylalkylidene)(indenyl)ruthenium(II) Complexes: Synthesis by Protonation of Alkenyl Derivatives

“…Complex 2 was isolated as an air-stable yellow solid and has been characterized by elemental analysis, IR and NMR ( 1 H, 13 C{ 1 H} and 31 P{ 1 H}) spectroscopy, which support the proposed formulation. The most significant signals arise from the presence of the two nonequivalent phosphorus nuclei: a) the hydride resonance which appears in the 1 H NMR spectrum as a triplet at δ ϭ Ϫ14.33 (t, 2 J H,P ϭ 2 J H,PЈ ϭ 29.8 Hz) and b) two doublet resonances in the 31 P{ 1 H} spectrum at δ ϭ 101.22 and 101.73 ( 2 J P,PЈ ϭ 87.6 Hz) typical of an AB system.…”

“…In particular, Figure 1. ORTEP-type diagram of [RuH(η 5 -C 9 H 7 ){κ 2 -P,P-(S)-peap}] (2) with ellipsoids drawn at a 30% probability; phenyl rings of the Ph 2 P groups in the diphosphazane have been omitted for clarity its 31 P{ 1 H} NMR spectrum shows two doublet signals at δ ϭ 83.2 and 91.4 ( 2 J P,PЈ ϭ 112.7 Hz) of an AB system, which is in agreement with the presence of two diastereo- [RuCl(η 5 -C 9 H 7 )(PPh 3 ) 2 ] ϩ (S)-peap Ǟ (1) [RuCl(η 5 -C 9 H 7 ){κ 2 -P,P-(S)-peap}] ϩ 2 PPh 3 According to the classical route for the synthesis of transition metal hydride derivatives based on the β-hydrogen elimination from a methoxide complex, [13] the hydride complex [RuH(η 5 -C 9 H 7 ){κ 2 -P,P-(S)-peap}] (2) has been prepared (85% yield) by treatment of complex 1 with an excess of NaOMe in refluxing methanol, see Equation (2).…”

“…13 C{ 1 H} NMR spectroscopic data [spectra recorded in C 6 D 6 ; δ in ppm and J C,P ϭ J C,PЈ in Hz (in parentheses); abbreviations: s, singlet; d, doublet; t, triplet; m, multiplet] for the alkenyl complexes 3, 4, 5 and vinylalkenyl complexes 6aϪd ethyl ether to give the (E)-alkenyl complex 3 (71% yield). Similarly, complex 2 reacted with an excess of the terminal alkynes methyl propiolate or phenylacetylene in toluene at 60 and 110°C, respectively, affording the alkenyl complexes 4 (66% yield) and 5 (73% yield), respectively (Scheme 2).…”

Some Ruthenium Derivatives of Penta-1,4-diyn-3-one

“…29 However, the attempted metalla-desilylation of (Me 3 SiC≡C) 2 CO with RuCl(PP)Cp' [(PP)Cp' = (PPh 3 ) 2 Cp, (dppe)Cp, (dppe)Cp*] using a range of conditions (KF, [NBu 4 ]F or NaOMe), 29,30 in the presence of salts of large anions ([NH 4 ]PF 6 , Na[BPh 4 ]), additional bases (NEt 3 , dbu) and in various solvents (MeOH, Bu t OH, thf) proved unsuccessful, only recovered starting material or RuH(PP)Cp' (from reaction of the chloro complex with alcohols / bases 31 ) having been obtained. It is likely that the presence of the electron-withdrawing ketone function deactivates the deprotected (HC≡C) 2 CO (which is also unstable under these reaction conditions) towards metallation.…”

Transfer Hydrogenation of Ketones Catalysed by New Half‐Sandwich Ruthenium(II) Complexes Bearing the Sulfonated Phosphane (meta‐Sulfonatophenyl)diphenylphosphane Potassium Salt (TPPMS)

“…[28] Thus, the reaction of [RuCl 2 (η 6 -p-cymene)(TPPMS)] (1a) with NaOMe in methanol yields the hydride derivative [RuClH(η 6 -p-cymene)(TPPMS)] (4) which can be isolated as a yellow solid in 63 % yield after work-up (Scheme 4).…”