US 2005/0043541 A1 · Metal complexes useful in metathesis and other reactions

Abstract

This invention provides metal complexes being useful as catalyst components in metathesis reactions and in reactions involving the transfer of an atom or group to an ethylenically or acetylenically unsaturated compound or another reactive substrate and, with respect to a sub-class thereof, for the polymerisation of α-olefins and optionally conjugated dienes, with high activity at moderate tempera-tures. It also provides methods for obtaining polymers with very narrow molecular weight distribution by means of a living reaction. It also provides methods for making said metal complexes and novel intermediates involved in such methods. It further provides derivatives of said metal complexes which are suitable for covalent bonding to a carrier, the product of such covalent bonding being useful as a supported catalyst for heterogeneous catalytic reactions. It also provides a direct one-step synthesis of pyrrole, furan and thiophene compounds from diallyl compounds.

Claims21

Dependent claims

A five-coordinate metal complex, a salt, a solvate or an enantiomer thereof, comprising a carbene ligand, a multidentate ligand and one or more other ligands, wherein at least one of said other ligands is a constraint steric hindrance ligand having a pKa of at least 15.

A five-coordinate metal complex being selected from metal complexes having one of the general formulae (IA) and (IB)

wherein:
M is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table;
Z is selected from the group consisting of oxygen, sulphur, selenium, NR″″, PR″″, AsR″″ and SbR″″;
R″, R′″ and R″″ are each a radical independently selected from the group consisting of hydrogen, C1-6 alkyl, C3-10 cycloalkyl, C1-6 alkyl-C1-6 alkoxysilyl, C1-6 alkyl-aryloxysilyl, C1-6 alkyl-C3-10 cycloalkoxysilyl, aryl and heteroaryl, or R″ and R′″ together form an aryl or heteroaryl radical, each said radical being optionally substituted with one or more, preferably 1 to 3, substituents R5 each independently selected from the group consisting of halogen atoms, C1-6 alkyl, C1-6 alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, C1-6 alkyl-C1-6 alkoxysilyl, C1-6 alkyl-aryloxysilyl, C1-6 alkyl-C3-10 cycloalkoxysilyl, alkylammonium and arylammonium;
R′ is either as defined for R″, R′″ and R″″ when included in a compound having the general formula (IA) or, when included in a compound having the general formula (IB), is selected from the group consisting of C1-6 alkylene and C3-8 cycloalkylene, the said alkylene or cycloalkylene group being optionally substituted with one or more substituents R5;
R1 is a constraint steric hindrance group having a pKa of at least 15;
R2 is an anionic ligand or a solvent, the complex being associated with an anion when R2 is a solvent;
R3 and R4 are each hydrogen or a hydrocarbon radical selected from the group consisting of C1-20 alkyl, C1-20 alkenyl, C1-20 alkynyl, C1-20 carboxylate, C1-20 alkoxy, C1-20 alkenyloxy, C1-20 alkynyloxy, aryl, aryloxy, C1-20 alkoxycarbonyl, C1-8 alkylthio, C1-20 alkylsulfonyl, C1-20 alkylsulfinyl C1-20 alkylsulfonate, arylsulfonate, C1-20 alkylphosphonate, arylphosphonate, C1-20 alkylammonium and arylammonium;
R′ and one of R3 and R4 may be bonded to each other to form a bidentate ligand;
R′″ and R″″ may be bonded to each other to form an aliphatic ring system including a heteroatom selected from the group consisting of nitrogen, phosphorous, arsenic and antimony;
R3 and R4 together may form a fused aromatic ring system, and
y represents the number of sp2 carbon atoms between M and the carbon atom bearing R3 and R4 and is an integer from 0 to 3 inclusive,
salts, solvates and enantiomers thereof.

10 more elements

A method of performing a reaction involving the transfer of an atom or group to an ethylenically or acetylenically unsaturated compound or another reactive substrate in the presence of a catalyst, wherein said catalyst comprises a five-coordinate metal complex having one of the general formulae (IC) and (ID)

or a cationic species thereof, optionally in combination with a supporting amount of a carrier, wherein:
M is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table;
Z is selected from the group consisting of oxygen, sulphur, selenium, NR″″, PR″″, AsR″″ and SbR″″;
R″, R′″ and R″″ are each a radical independently selected from the group consisting of hydrogen, C1-6 alkyl, C3-10 cycloalkyl, C1-6 alkyl-C1-6 alkoxysilyl, C1-6 alkyl-aryloxysilyl, C1-6 alkyl-C3-10 cycloalkoxysilyl, aryl and heteroaryl, or R″ and R′″ together form an aryl or heteroaryl radical, each said radical being optionally substituted with one or more, preferably 1 to 3, substituents R5 each independently selected from the group consisting of halogen atoms, C1-6 alkyl, C1-6 alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, C1-6 alkyl-C1-6 alkoxysilyl, C1-6 alkyl-aryloxysilyl, C1-6 alkyl-C3-10 cycloalkoxysilyl, alkylammonium and arylammonium;
R′ is either as defined for R″, R′″ and R″″ when included in a compound having the general formula (IA) or, when included in a compound having the general formula (IB), is selected from the group consisting of C1-6 alkylene and C3-8 cycloalkylene, the said alkylene or cycloalkylene group being optionally substituted with one or more substituents R5;
R2 is an anionic ligand or a solvent, the complex being associated with an anion when R2 is a solvent;
R3 and R4 are each hydrogen or a hydrocarbon radical selected from the group consisting of C1-20 alkyl, C1-20 alkenyl, C1-20 alkynyl, C1-20 carboxylate, C1-20 alkoxy, C1-20 alkenyloxy, C1-20 alkynyloxy, aryl, aryloxy, C1-20 alkoxycarbonyl, C1-8 alkylthio, C1-20 alkylsulfonyl, C1-20 alkylsulfinyl C1-20 alkylsulfonate, arylsulfonate, C1-20 alkylphosphonate, arylphosphonate, C1-20 alkylammonium and arylammonium;
R′ and one of R3 and R4 may be bonded to each other to form a bidentate ligand;
R′″ and R″″ may be bonded to each other to form an aliphatic ring system including a heteroatom selected from the group consisting of nitrogen, phosphorous, arsenic and antimony;
R3 and R4 together may form a fused aromatic ring system;
y represents the number of sp2 carbon atoms between M and the carbon atom bearing R3 and R4 and is an integer from 0 to 3 inclusive;
and
R16 is a neutral electron donor.

10 more elements

A derivative, being suitable for covalent bonding to a carrier, of a five-coordinate metal complex being selected from metal complexes having one of the general formulae (IA) and (IB)

wherein:
M is a transition metal selected from the group consisting of groups 4, 5, 6, 7, 8, 9, 10, 11 and 12 of the Periodic Table;
Z is selected from the group consisting of oxygen, sulphur, selenium, NR″″, PR″″, AsR″″ and SbR″″;
R″, R′″ and R″″ are each a radical independently selected from the group consisting of hydrogen, C1-6 alkyl, C3-10 cycloalkyl, C1-6 alkyl-C1-6 alkoxysilyl, C1-6 alkyl-aryloxysilyl, C1-6 alkyl-C3-10 cycloalkoxysilyl, aryl and heteroaryl, or R″ and R′″ together form an aryl or heteroaryl radical, each said radical being optionally substituted with one or more, preferably 1 to 3, substituents R5 each independently selected from the group consisting of halogen atoms, C1-6 alkyl, C1-6 alkoxy, aryl, alkylsulfonate, arylsulfonate, alkylphosphonate, arylphosphonate, C1-6 alkyl-C1-6 alkoxysilyl, C1-6 alkyl-aryloxysilyl, C1-6 alkyl-C3-10 cycloalkoxysilyl, alkylammonium and arylammonium;
R′ is either as defined for R″, R′″ and R″″ when included in a compound having the general formula (IA) or, when included in a compound having the general formula (IB), is selected from the group consisting of C1-6 alkylene and C3-8 cycloalkylene, the said alkylene or cycloalkylene group being optionally substituted with one or more substituents R5;
R1 is a constraint steric hindrance group having a pKa of at least 15;
R2 is an anionic ligand or a solvent, the complex being associated with an anion when R2 is a solvent;
R3 and R4 are each hydrogen or a hydrocarbon radical selected from the group consisting of C1-20 alkyl, C1-20 alkenyl, C1-20 alkynyl, C1-20 carboxylate C1-20 alkoxy, C1-20 alkenyloxy, C1-20 alkynyloxy, aryl, aryloxy, C1-20 alkoxycarbonyl, C1-8 alkylthio, C1-20 alkylsulfonyl, C1-20 alkylsulfinyl C1-20 alkylsulfonate, arylsulfonate, C1-20 alkylphosphonate, arylphosphonate, C1-20 alkylammonium and arylammonium;
R′ and one of R3 and R4 may be bonded to each other to form a bidentate ligand;
R′″ and R″″ may be bonded to each other to form an aliphatic ring system including a heteroatom selected from the group consisting of nitrogen, phosphorous, arsenic and antimony;
R3 and R4 together may form a fused aromatic ring system, and
y represents the number of sp2 carbon atoms between M and the carbon atom bearing R3 and R4 and is an integer from 0 to 3 inclusive, salts, solvates and enantiomers thereof, and
wherein R′ and/or R″ is replaced or substituted with a group having the formula:
R20—(CH2)n—D—Si—R21R22R23 (VII),
wherein:
R20 is a radical selected from the group consisting of C1-6 alkylene, arylene, heteroarylene and C3-8 cycloalkylene, the said radical being optionally substituted with one or more R24 substituents each independently selected from the group consisting of C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C1-20 carboxylate, C1-20 alkoxy, C2-20 alkenyloxy, C2-20 alkynyloxy, C2-20 alkoxycarbonyl, C1-20 alkylsulfonyl, C1-20 alkynylsulfinyl, C1-20 alkylthio, aryloxy and aryl;
D is a divalent atom or radical selected from the group consisting of oxygen, sulphur, silicon, arylene, methylene, CHR24, C(R24)2, NH, NR24 and PR24;
R21, R22 and R23 are each independently selected from the group consisting of hydrogen, halogen and R24;
and
n is an integer from 1 to 20;
provided that at least one of R21, R22 and R23 is selected from the group consisting of C1-20 alkoxy, C2-20 alkenyloxy, C2-20 alkynyloxy, C2-20 alkoxycarbonyl, C1-20 alkylsulfonyl, C1-20 alkynylsulfinyl, C1-20 alkylthio and aryloxy.

18 more elements

Dependencies are inferred from the claim text.

Metal complexes useful in metathesis and other reactions

Life of this patent

Metal complexes useful in metathesis and other reactions

Life of this patent

Abstract

Claims21