Patent GB-1159906-A (GB)
Title: New Ruthenim Complexes and Processes for their Preparation.
IPC: C07F15/00
Filed: 1968-03-22
Abstract: 1,159,906. Ruthenium complexes; organometallic compounds. RHONE-POULENC S.A. 22 March, 1968 [23 March, 1967; 11 April, 1967; 29 June, 1967; 11 Dec., 1967], No. 14059/68. Headings C2C and C2J. Novel ruthenium complexes are of the formula in which Diket represents a #-diketone residue, L represents a mono- or poly-dentate ligand other than a #-diketone, x and z are positive integers, y is zero or a positive integer and x+y+z=3. The residue Diket is preferably the residue of formula in which R<SP>1</SP> and R<SP>3</SP> are each 1-4 carbon alkyl, 1-4 carbon perfluoroalkyl, phenyl or naphthyl, R<SP>2</SP> is hydrogen or 1-4 carbon alkyl, and R<SP>1</SP> and R<SP>3</SP>, or R<SP>1</SP> and R<SP>2</SP>, or both R<SP>1</SP> and R<SP>2</SP> and R<SP>2</SP> and R<SP>3</SP> may be joined together to form a saturated cycloaliphatic 5- or 6-membered ring. Examples of such #-diketones include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 5 - methyl - 2,4 - hexanedione; 3,5 - heptanedione; 1,1,1 - trifluoro - 2,4 - pentanedione, benzoylacetone, dibenzoylacetone, 1 - naphthoyl - 3,3,3 - trifluoropropane - 2 - one, 1,3- cyclopentanedione, 1,3 - cyclohexanedione, 2 - acetylcyclohexanone and 1,8 - decahydronaphthalenedione. The ligand L may be taken from Lewis bases which include polyamines and monoamines, aldehydes, imines, amides, nitriles, tertiary phosphines, arsines and stibines, monoolefinic or polyolefinic compounds and heterocyclic bases. The compounds in which x=1, y=0 and z=2 may be obtained by reacting a tris-(#-dionato) ruthenium complex of formula Ru(Diket) 3  with a compound capable of furnishing a carbonyl group such as alcohols, amides, aldehydes and acid chlorides, in the presence of an inert hydrocarbon solvent and at a temperature between 20‹ and 200‹ C. The compounds in which x=y=z=1 may be prepared by reacting a ligand L with a #-dionatoruthenium carbonyl complex of formula [Ru(Diket) 2 (CO)] 2  or by replacing the ligand L<SP>1</SP> in a complex of formula [Ru(Diket) 2 (CO)L<SP>1</SP>] by another ligand L having a greater ability to donate an electron pair, in each case using a hydrocarbon or excess ligand as solvent. The compounds in which x=2, y=0 and z= 1 may be prepared by reacting a tris-(#-dionato) ruthenium of the formula Ru(Diket) 3  with carbon monoxide under a pressure of 5 to 100 bars in the presence of a hydrocarbon or an ether solvent and advantageously containing a ruthenium activator such as hydrated ruthenium oxide, a ruthenium carbonyl or finely divided metallic ruthenium optionally deposited on a carrier, which activator, expressed as ruthenium, is preferably present in a quantity equal to 0À001 to 10% of the weight of ruthenium in the original tris-(#-dionato) ruthenium complex. The compounds of formula [Ru(Diket) 2 (CO) 2 ] may also be prepared by reacting any one of the complexes of formulµ [Ru(Diket) 2 (CO)] 2 ; [Ru(Diket) 2 (CO)L] or [Ru(Diket) 2 L 2 ] with carbon monoxide under at least atmospheric pressure and preferably under 5 to 100 bars in the presence of a hydrocarbon or an ether solvent. The complex of formula Ru(Diket) 2 L 2  may be prepared by reacting a ligand L with a tris-(#-dionato) ruthenium complex under a hydrogen atmosphere and in the presence of a hydrogenation catalyst, particularly ruthenium based, optionally in the presence of a solvent. The #-diketone used in the examples is acetylacetone. In Example 1 ruthenium acetylacetonate is prepared by refluxing RuCl 3  with acetylacetone and water keeping the pH at 7 by addition of sodium bicarbonate. In Example 3, the complex Ru(C 5 H 7 O 2 ) 2 (CO)(CH 3 CN) is reacted with acrylonitrile (stabilized with 0À05% of hydroquinone) under constant hydrogen pressure and a mixture of linear dimers, 1,4-dicyanobutenes and adiponitrile are formed.