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• 35798-09-5 {Ru(CO)H(MeCN)2(PPh₃)2}ClO₄ 

Relevant academic research and scientific papers

Synthesis of new ruthenium(II) carbonyl hydrido, alkenyl, and alkynyl complexes with chelating diphosphines

Substitution of one or two triphenylphosphine ligands of Ru(CO)ClH(PPh3)3 by bidentate diphosphines Ph2P(CH2)nPPh2 (L-L) (n = 1, dppm; n = 2, dppe; n = 3, dppp; n = 4, dppb) or 1,1′-bis(diphenylphosphino)ferrocene (dppf) led to hydrides Ru(CO)ClH(PPh3)2(L-L) or Ru-(CO)ClH(PPh3)(L-L). The hydrido complexes were characterized spectroscopically and by one X-ray structure. Hydride Ru(CO)ClH(PPh3)(dppf) crystallizes in the monoclinic space group P21/n, with a = 17.768(1) ?, b = 25.252(2) ?, c = 11.213(1) ?, β = 92.83(1)°, Z = 4, and V = 4459.3(6) ?3. Reaction of Ru(CO)ClH(PPh3)3 or [Ru(CO)H(MeCN)2(PPh3)2]+PF6-with 2 equiv of diphosphines L-L led to [Ru(CO)H(L-L)2]+A- (L-L = dppm, dppe, dppp) (A = Cl, PF6). Hydrides Ru(CO)ClH(PPh3)2(L-L) react with 1-alkynes to give alkenyl complexes Ru(CO)Cl(CH=CHR)(PPh3)(L-L) with a chelating diphosphine ligand. Ru(CO)ClH(PPh3)-(L-L) gave σ-alkynyl complexes Ru(CO)Cl(C≡CR)L(L-L) directly in their reactions with 1-alkynes. The hydride with dppb as the ligand showed the highest reactivity. The preparation of hexacoordinated alkenyl derivatives Ru(CO)Cl(CH=CHR)(PPh3)(L-L) with a chelating diphosphine was carried out by treatment of other alkenyl derivatives with the diphosphines. Surprisingly, reaction of alkenyls Ru(CO)Cl(CH=CHR)(Me2Hpz)(PPh3)2 (R = CMe3, P-MeC6H4) with dppf led to complexes Ru(CO)Cl(CH=CHR)(Me2Hpz)(dppf) by substitution of both PPh3 ligands instead of the dimethylpyrazole. Ruthenium alkenyls Ru-(CO)Cl(CH=CHR)L(dppf) (L = Me2Hpz, PPh3) react cleanly with 1-alkynes at room temperature to give alkynyl complexes Ru(CO)Cl(C=CR)L(dppf) in good yield. This reaction was applied to the synthesis of a bimetallic complex Ru(CO)Cl(PPh3)(dppf)(C≡C-p-C6H 4C≡C)-Ru(CO)Cl(PPh)(dppf) as a mixture of meso and dl diastereomers.