Monocarbonyl ruthenium and osmium catalysts

A pentacoordinate or hexacoordinate complex of formula (1):

• [MXYa(CO)LbL′c]Wd (1)
• wherein:
• M is Ru or Os;
• a, b and d are, independently, 0 or 1;
• c is 1 or 2;
• X and Y are, independently, a halide, hydride, C1-C20 carboxylate or C1-C20 alkoxide;
• W is a halide, C1-C20 carboxylate or C1-C20 alkoxide;
• L is a nitrogen-containing ligand that is:
• (I) a NN compound of formula Ia to Ic:
• (II) a HCNN compound of formula IIa-IIb and a CNN compound of formula IIc-IId:
• (III) a HCN compound of formula IIIa
• wherein
• R1-R15 are, independently, H, C1-C20 aliphatic group or C5-C20 aromatic group;
• L′ is at least one phosphorus-containing ligand that is:
• a phosphine (P) that is:
• a phosphine of formula PR16R17R18, wherein R16-R18 are, independently, H, C1-C20 aliphatic group or C5-C20 aromatic group;
• or an optically active phosphine that is (S)-neomenthyldiphenylphosphine or (R)-(+)-2-(diphenylphosphino)-2′-methoxy-1,1′-binaphthyl,
• a diphosphine (PP) that is:
• a diphosphine of formula P(R19)2—Z—P(R20)2, wherein Z is a C2-C4 aliphatic group or ferrocene optionally substituted with a C1-C20 aliphatic group, and wherein R19 and R20 are, independently, C1-C20 aliphatic group or C5-C20 aromatic group;
• or an optically active diphosphine that is (R)-(6,6′-dimethoxybiphenyl-2,2′-diyl)bis(diphenylphosphine], (R)-(1,1′-binaphthalene-2,2′-diyl)bis(diphenylphosphine), (R)-(1,1′-binaphthalene-2,2′-diyl)bis[bis(3,5-dimethylmethyl)phosphine], (R)-1-{-2-[diphenylphosphine]ferrocenyl}ethyldicyclohexyl phosphine, (R)-1-{-2-[bis(3,5-dimethyl-4-methoxyphenyl)phosphine]ferrocenyl}ethyldicyclohexyl phosphine or (2R,4R)-2,4-bis(diphenylphosphine)pentane;
• a HCP compound of formula (IVa) and a CP ligand of formula (IVb)
• a PNN compound of formula (V)
• wherein
• R21-R29 are, independently, H, C1-C20 aliphatic group or C5-C20 aromatic group;
• provided that:
• when a, b, and c are 1;
• d is 0;
• X and Y are Cl, L is ethylenediamine or 2-(aminomethyl)pyridine or 2,2′-bipyridine or 4,4′-dimethyl-2,2′-bipyridine, L′ is not a phosphine (P) of formula PR16R17R18 in which R16, R17, and R18 are the same and are phenyl or p-tolyl,
• when a is 0;
• b, c, and d are 1;
• X and W are Cl or X is H and W is Cl, L is ethylenediamine or 2-(aminomethyl)pyridine, L′ is not Ph2P(CH2CH2CH2)PPh2;
• when a and d are 0;
• b and c are 1;
• X is Cl, L is ethylenediamine or 2-(aminomethyl)pyridine, L′ is not a ligand (CP) of formula (IVb) in which R21 and R22 are phenyl and R23 is methyl;
• and
• when a, b and d are 0, c is 2, X is Cl and R23 is —CH3, R21 and R22 are not phenyl groups.