Transition metal complexes having 2,2'-bipyridine ligands substituted by at least one ammonium alkyl radical

• US 5,410,059 A
• Filed: 12/14/1993
• Issued: 04/25/1995
• Est. Priority Date: 12/15/1992
• Status: Expired due to Term

• Current Assignee: Asulab SA (The Swatch Group AG)
• Original Assignee: Asulab SA (The Swatch Group AG)
• Inventors: Graetzel, Michael, Fraser, David, Zakeeruddin, Shaik M.
• Primary Examiner(s): Ivy, C. Warren
• Assistant Examiner(s): NORTHINGTON DAVIS, ZINNA
• Application Number:
  US08/166,977
• Time in Patent Office: 497 Days
• Field of Search: 546/10
• US Class Current: 546/10
• CPC Class Codes: C07D 213/22 containing two or more pyridine rings directly linked together, e.g. bipyridyl
• CPC Class Codes: C07F 15/0026 without a metal-carbon linkage
• CPC Class Codes: C07F 15/0053 without a metal-carbon linkage
• CPC Class Codes: C07F 15/025 without a metal-carbon linkage
• CPC Class Codes: C12Q 1/004 mediator-assisted
• CPC Class Codes: H10K 85/344 comprising ruthenium

Abstract

Complexes of the general formula I ##STR1## wherein R₁, R₂ and R₃, which may be the same or different, each represent a straight or branched alkyl radical having 1 to 5 carbon atoms or together with the adjacent nitrogen atom a heterocyclic radical having 5 to 7 carbon atoms; "alk" represents a straight or branched alkylene radical having 1 to 5 carbon atoms; R₄ to R₈, which may be the same or different, represent hydrogen, or a hydroxy, alkoxy, aryloxy or primary secondary or tertiary amino group, or the group -alk-N⁺ (R₁ R₂ R₃) wherein "alk", R₁, R₂ and R₃ have the meanings given above; M represents a transition metal such as Fe, Ru or Os; X represents an anion and n is an integer corresponding to the number of positive charges of the complex.

Claims

1. A transition metal complex having three bidentate ligands at least two of which are substituted in the 4,4'"'"' position by quaternary ammonium alkyl groups with the formula ##STR6## wherein R₁, R₂, and R₃ may be the same or different and each represents a straight chain or branched chain alkyl group having 1 to 5 carbon atoms or taken together with the adjacent nitrogen atom represent a heterocyclic radical having 5 to 7 carbon atoms;

alk represents a straight chain or branched alkylene radical having 1 to 5 carbon atoms;

R₄ represents the group -alk-N⁺ R₁ R₂ R₃ wherein alk, R₁, R₂, and R₃ have the meanings given above;

R₅ to R₈, which may be the same or different, represent hydrogen, or a hydroxy, alkoxy, aryloxy or primary, secondary or tertiary amino group or the group -alk-N⁺ (R₁ R₂ R₃) wherein alk, R₁, R₂, and R₃ have the meanings given above;

M represents a transition metal selected from iron, ruthenium or osmium;

x represents an anion selected from Cl, PF₆^-, BR^-, or BF₄^- and n is an integer corresponding to the number of positive charges of the ligands and of the transition metal.

2. A complex according to claim 1 wherein the alkylene radical alk represents a methylene radical -CH₂ -.

3. A complex according to claim 1 wherein -N(R₁ R₂ R₃) represents the triethylammonium group and corresponds to the formula III ##STR7## wherein R₅, R₆, R₇, R₈, X and n have the same meanings as those given for the general formula I.

4. A complex according to claim 3 which corresponds to one of the compounds of formula

osmium bis[4,4'"'"'-bisamino-2,2'"'"'-bipyridine]-mono[4,4'"'"'-bis(triethylammoniummethyl)-2,2'"'"'-bipyridine, hereinafter referred to as Os(DA-bpy)₂ (TEAM-bpy) or salts thereof,

ruthenium bis[4,4'"'"'-bisamino-2,2'"'"'-bipyridine 4,4'"'"'-bis(triethylammoniummethyl)-2,2'"'"'-bipyridine, hereinafter referred to as Ru(DA-bpy)₂ (TEAM-bpy) or salts thereof,

ruthenium bis[4,4'"'"'-bis(dimethylamino-2,2'"'"'-bipyridine]mono[4,4'"'"'-bis(triethylammoniummethyl)-2,2'"'"'-bipyridine], hereinafter referred to as Ru(DMA-bpy)₂ (TEAM-bpy) or salts thereof,

osmium bis[4,4'"'"'-bis(triethylammoniummethyl) 2,2'"'"'-bipyridine]mono[4,4'"'"'-bisamino) 2,2'"'"'-bipyridine, hereinafter referred to as Os(TEAM-bpy)₂ (DA-bpy) or salts thereof,

osmium tris [4,4'"'"'-bis(triethylammoniummethyl)-2,2'"'"'-bipyridine], hereinafter referred to as Os(TEAM-bpy)₃, or salts thereof,

iron tris [4,4'"'"'-bis(triethylammoniummethyl)-2,2'"'"'-bipyridine], hereinafter referred to as Fe(TEAM-bpy)₃, or salts thereof.

5. A complex according to claim 1 wherein -N(R₁ R₂ R₃) represents the N-pyridino group and has the formula IV ##STR8## wherein R₅, R₆, R₇, R₈, X and n have the same meanings as those given for formula I.

6. A complex according to claim 5, which corresponds to one of the compounds of formula

osmium bis[4,4'"'"'-bisamino-2,2'"'"'-bipyridine]-mono[4,4'"'"'-bis(N-pyridiniummethyl)-2,2'"'"'-bipyridine], hereinafter referred to as Os(DA-bpy)₂ (NPM-bpy) or salts thereof,

ruthenium bis[4,4'"'"'-bisamino-2,2'"'"'-bipyridine]-mono[4,4'"'"'-bis(N-pyridiniummethyl)-2,2'"'"'-bipyridine, hereinafter referred to as Ru(DA-bpy)₂ (NPM-bpy) or salts thereof,

osmium bis[4,4'"'"'-bis(N-pyridiniummethyl)-2,2'"'"'-bipyridine]mono[4,4'"'"'-bisamino-2,2'"'"'-bipyridine), hereinafter referred to as Os(NPM-bpy)₂ (DA-bpy) or salts thereof,

osmium tris [4,4'"'"'-bis(N-pyridiniummethyl) 2,2'"'"'-bipyridine], hereinafter referred to as Os(NPM-bpy)₃, or salts thereof,

iron tris [4,4'"'"'-bis(N-pyridiniummethyl)-2,2'"'"'-bipyridine], hereinafter referred to as Fe(TEAM-bpy)₃, or salts thereof.

7. A complex according to claim 1 wherein the transition metal is osmium.

8. A complex according to claim 1 wherein the transition metal is ruthenium.

9. A complex according to claim 1 wherein the transition metal is iron.

10. A complex according to claim 1 wherein the salt is a chloride or a hexafluorophosphate.