Metal complexes useful in metathesis and other reactions

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 ruthenium and osmium;
• 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 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 ligand having a pKa of at least 15;
• R2 is an anionic ligand;
• 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 and enantiomers thereof.

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

• wherein:
• M is a transition metal selected from the group consisting of ruthenium and osmium;
• Z is selected from the group consisting of oxygen, sulphur, selenium, NR″″, PR″″, AsR″″, and SbR″″;
• wherein R′ and/or R″ is replaced or substituted with a group having the formula:
• —R20—(CH2)n—D—Si—R21R22R23 (VIII),
• 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;
• 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 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, or R″ is a group of Formula (VIII);
• 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, or R′ is a group of Formula (VIII);
• R1 is a constraint steric hindrance ligand having a pKa of at least 15;
• R2 is an anionic ligand;
• 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, aryiphosphonate, 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, and enantiomers thereof.