Hydroformylation

A process for hydroformylating compounds which contain at least one ethylenically unsaturated double bond by reacting with carbon monoxide and hydrogen in the presence of a catalyst comprising at least one complex of a metal of transition group VIII of the Periodic Table of the Elements with ligands which each have a phosphorus group and at least one functional group which is capable of forming intermolecular noncovalent bonds, wherein the complex has ligands which are dimerized via intermolecular noncovalent bonds and wherein the distance between the phosphorus atoms of the dimerized ligands is at most 5 Å, and wherein the ligands include at least one structural element of the general formulae I.a or I.b

• or tautomers thereof where
• R1 and R2 are each independently alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy,
• R3 is hydrogen or is as defined for R1 and R2,
• X is a bivalent bridging group having from 1 to 5 bridging atoms between the flanking bonds,
• Y is O, S or NR4, where R4 is hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
• and two or more than two of the X radicals and R1 to R4 together with the structural element of the formula I.a or I.b to which they are bonded may be a mono- or polycyclic compound.

A process for hydroformylating compounds which contain at least one ethylenically unsaturated double bond by reacting with carbon monoxide and hydrogen in the presence of a catalyst comprising at least one complex of a metal of transition group VIII of the Periodic Table of the Elements with ligands which each have a phosphorus group and at least one functional group which is capable of forming intermolecular noncovalent bonds, wherein the complex has ligands which are dimerized via intermolecular noncovalent bonds and wherein the distance between, the phosphorus atoms of the dimerized ligands is at most 5 Å, and wherein the ligands are selected from compounds of the general formulae I.1 to I.3

• and the tautomers thereof where
• one of the R5 to R9 radicals is a group of the formula —W′—PR1R2 where
• W′ is a single bond, a heteroatom, a heteroatom-containing group or a bivalent bridging group having from 1 to 4 bridging atoms between the flanking bonds,
• R1 and R2 are each independently alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy,
• the R5 to R9 radicals which are not —W′—PR1R2 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCOORo, WCOO−M+, W(SO3)Ro, W(SO3)−M+, WPO3(Ro)(Rp), W(PO3)2−(M+)2, WNE1E2, W(NE1E2E3)+X−, WORq, WSRq, (CHRrCH2O)xRq, (CH2NE1)xRq, (CH2CH2NE1)xRq, halogen, nitro, acyl or cyano,
• where
• W is a single bond, a heteroatom, a heteroatom-containing group or a bivalent bridging group having from 1 to 20 bridging atoms,
• Ro and Rp are each identical or different radicals selected from alkyl, cycloalkyl, aryl and hetaryl,
• Rq, E1, E2, E3 are each identical or different radicals selected from hydrogen, alkyl, cycloalkyl, acyl, aryl and hetaryl,
• Rr is hydrogen, methyl or ethyl,
• M+ is one cation equivalent,
• X− is one anion equivalent and
• x is an integer from 1 to 240,
• and in each case two adjacent R5, R6, R7, R8 and R9 radicals, together with the ring carbon atoms to which they are bonded, may also be a fused ring system having 1, 2 or 3 further rings, and
• Ra and Rb are each hydrogen, alkyl, acyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

A process for hydroformylating compounds which contain at least one ethylenically unsaturated double bond by reacting with carbon monoxide and hydrogen in the presence of a catalyst comprising at least one complex of a metal of transition group VIII of the Periodic Table of the Elements with ligands which are selected from compounds of the general formulae I.1 to I.3

• and the tautomers thereof where
• one of the R5 to R9 radicals is a group of the formula —W′—PR1R2 where
• W′ is a single bond, a heteroatom, a heteroatom-containing group or a bivalent bridging group having from 1 to 4 bridging atoms between the flanking bonds,
• R1 and R2 are each independently alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy,
• the R5 to R9 radicals which are not —W′—PR1R2 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCOORo, WCOO−M+, W(SO3)Ro, W(SO3)−M+, WPO3(Ro)(Rp), W(PO3)2−(M+)2, WNE1E2, W(NE1E2E3)+X−, WORq, WSRq, (CHRrCH2O)xRq, (CH2NE1)xRq, (CH2CH2NE1)xRq, halogen, nitro, acyl or cyano,
• where
• W is a single bond, a heteroatom, a heteroatom-containing group or a bivalent bridging group having from 1 to 20 bridging atoms,
• Ro and Rp are each identical or different radicals selected from alkyl, cycloalkyl, aryl and hetaryl,
• Rq, E1, E2, E3 are each identical or different radicals selected from hydrogen, alkyl, cycloalkyl, acyl, aryl and hetaryl,
• Rr is hydrogen, methyl or ethyl,
• M+ is one cation equivalent,
• X− is one anion equivalent and
• x is an integer from 1 to 240,
• and in each case two adjacent R5, R6, R7, R8 and R9 radicals, together with the ring carbon atoms to which they are bonded, may also be a fused ring system having 1, 2 or 3 further rings, and
• Ra and Rb are each hydrogen, alkyl, acyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.