Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof

A Ruthenium complex represented by the structure of any of formulae A1, A2 or A3:

• wherein
• L1 is selected from the group consisting of phosphine (PRaRb), phosphite P(ORa)(ORb), phosphinite P(ORa)(Rb), amine (NRaRb), imine, oxazoline, sulfide (SRa), sulfoxide (S(═O)Ra), heteroaryl containing at least one heteroatom selected from nitrogen and sulfur;
• arsine (AsRaRb), stibine (SbRaRb) and a N-heterocyclic carbene represented by the structures:
• L2 is a mono-dentate two-electron donor selected from the group consisting of CO, PRaRbRc, P(ORa)(ORb)(ORc), NO+, AsRaRbRc, SbRaRbRc, SRaRb, nitrile (RCN), isonitrile (RNC), N2, PF3, CS, heteroaryl, tetrahydrothiophene, alkene and alkyne;
• L3 is absent or is L2;
• Y and Z are each independently H or an anionic ligand selected from the group consisting of H, halogen, OCOR, OCOCF3, OSO2R, OSO2CF3, CN, OR, N(R)2 and RS;
• Ra, Rb and Rc are each independently alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl or alkylheteroaryl;
• R, R1, R2 and R3 are each independently H, alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl or alkylheteroaryl;
• X1 represents zero, one, two or three substituents and X2 represents zero, one, two, three or four substituents, wherein each such substituent is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl, alkylheteroaryl, halogen, nitro, amide, ester, cyano, alkoxy, alkylamino, arylamino, an inorganic support and a polymeric moiety;
• and
• anion represents a group bearing a single negative charge;
• or
• a borane derivative of said catalyst.

A borane derivative of a Ruthenium complex, wherein said borane derivative is represented by the structure of formula F:

• wherein
• each L1 is independently selected from the group consisting of phosphine (PRaRb), phosphite P(ORa)(ORb), phosphinite P(ORa)(Rb), amine (NRaRb), imine, oxazoline, sulfide (SRa), sulfoxide (S(═O)Ra), heteroaryl containing at least one heteroatom selected from nitrogen and sulfur;
• arsine (AsRaRb), stibine (SbRaRb) and a N-heterocyclic carbene represented by the structures:
• L3 is absent or is a mono-dentate two-electron donor selected from the group consisting of CO, PRaRbRc, P(ORa)(ORb)(ORc), NO+, AsRaRbRc, SbRaRbRc, SRaRb, nitrile (RCN), isonitrile (RNC), N2, PF3, CS, heteroaryl and tetrahydrothiophene;
• L4 is —CH2-L1- or a group of the formula:
• Ra, Rb and Rc are each independently alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl or alkylheteroaryl;
• R, R1, R2 and R3 are each independently H, alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl or alkylheteroaryl;
• X1 represents zero, one, two or three substituents and X2 represents zero, one, two, three or four substituents, wherein each such substituent is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl, alkylheteroaryl, halogen, nitro, amide, ester, cyano, alkoxy, alkylamino, arylamino, an inorganic support and a polymeric moiety.

A process for preparing a carboxylic acid comprising the step of reacting a primary alcohol with water and a base in the presence of the Ruthenium complex represented by the structure of any one of formulae A1′, A2′ or A3′

• wherein
• L1 and L2 are each independently selected from the group consisting of nucleophilic carbene (:C(R)2), P(R)2, P(OR)2, N(R)2, imine, SR, SH, S(═O)R, heteroaryl wherein the heteroatom is selected from nitrogen and sulfur, As(R)2, Sb(R)2 and an N-heretocyclic carbene represented by the structure:
• wherein each of R, R2 and R3 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, alkylaryl, heterocyclyl and heteroaryl;
• L3 is a mono-dentate two-electron donor selected from the group consisting of CO, P(R)3, P(OR)3, NO+, As(R)3, Sb(R)3, S(R)2, nitrile (RCN) and isonitrile (RNC) wherein R is as defined above;
• L4 is absent or is L3;
• Y and Z are each independently H or an anionic ligand selected from the group consisting of halogen, OCOR, OCOCF3, OSO2R, OSO2CF3, CN, OH, OR, N(R)2, RS and SH;
• wherein R is as defined above;
• X represents zero, one, two or three substituents selected from the group consisting of alkyl, aryl, halogen, nitro, amide, ester, cyano, alkoxy, cycloalkyl, alkylaryl, heterocyclyl, heteroaryl, an inorganic support and a polymeric moiety;
• and
• anion represents a group bearing a single negative charge.