847481-94-1

Upstream product

• 109-77-3 malononitrile 
• 847481-92-9 OsH(NCCHCN)(2,3-diamino-2,3-dimethylbutane)(triphenylphosphine)2 

Relevant academic research and scientific papers

Probing the effect of the ligand X on the properties and catalytic activity of the complexes RuHX(diamine)(PPh3)2 (X = OPh, 4-SC 6H4OCH3, OPPh2, OP(OEt)2, CCPh, NCCHCN, CH(COOMe)2; diamine = 2,3-Diamino-2,3-dimethylbutane, (R,R)-1,2-Diaminocyclohexane)

The reactivity of the ruthenium-amido bond in RuH(NH2CMe 2CMe2NH)(PPh3)2 (1) toward weak acids HX and the influence of the X group on the catalytic activity of the resulting complex are explored here. Complex 1 reacts with the weak acids HX (X = OPh, 4-SC6H4OMe, OPPh2, OP(OEt)2, CCPh, NCCHCN, CH(COOMe)2) to form complexes of the type RuHX(tmen)(PPh3)2 (tmen = 2,3-diamino-2,3-dimethylbutane). The complexes with X = PhOH...OPh, 4-SC6H4OMe, OP(OEt)2, CCPh, CH-(COOMe)2 have been characterized by X-ray crystallography. The X group is situated trans to the hydride in all cases and is bonded to ruthenium via the donor atoms O, S, P, C, and O, respectively. The phenol in the phenoxide adduct RuH(PhOH...OPh)(tmen)(PPh 3)2 bridges via hydrogen bonds between the alkoxide oxygen and an amino hydrogen to form a six-membered RuO...HO...HN ring. One carbonyl oxygen of the malonate bonds to the Ru, while the other accepts a hydrogen bond from an amino hydrogen. The analogous complexes RuHX(dach)(PPh3)2 (dach = (R,R)-1,2-diaminocyclohexane) were synthesized by the reaction of RuHCl(dach)(PPh3)2 (2) with an equimolar amount of potassium tert-butoxide and HX. For all of the complexes the Ru-H vibrational frequency and the 1H NMR chemical shift of Ru-H correlate with the electronegativity of the trans atom X. The amido complex 1 and the complexes with X = CH(COOMe)2 and OPh are active catalysts for the Michael addition of dimethyl malonate to 2-cyclohexen-1-one. RuH(NCCHCN)(tmen)(PPh3)2 reacts with the Michael acceptor 2-cyclohexen-1-one to give RuH(NCC(C6H 9O)CN)(tmen)(PPh3)2, a trapped Michael adduct that has been characterized by X-ray crystallography. On the basis of these observations a catalytic cycle for the Michael addition reactions is proposed that involves the addition of the C-H bond of the Michael donor to the Ru-N bond followed by attack on the Michael acceptor and elimination of the Michael adduct, possibly by a 1,3-proton migration as observed for the malononitrile adduct. Only the complexes with X = H, CCPh are catalysts or precatalysts for the hydrogenation of neat acetophenone to 1-phenylethanol in the absence of added base under 10 atm of H2 at 20°C. Evidence is provided that the phenylacetylide complexes are precatalysts that are converted to the active trans-dihydride catalysts (X = H).

Reactions of an amido hydrido complex of osmium, OsH(NHCMe 2CMe2NH2)(PPh3)2: HX addition, HX transfer, and ketone H2 Hydrogenation

Summary: The new amido complex OsH(NHCM2CMe2 NH 2(PPh3)2 (2) reacts with weak acids HX to give complexes OsHX(tmen)(PPh3) (1; X = Cl, 3; X = NCCHCN; and X = H; tmen = NH2CM2