Platinum complexes carbonyl compounds

Consequently, by choosing proper conditions, especially the ratios of the carbonyl compound to the amino compound, very good yields of the desired amines can be obtained [322, 953]. In catalytic hydrogenations alkylation of amines was also achieved by alcohols under the conditions when they may be dehydrogenated to the carbonyl compounds [803]. The reaction of aldehydes and ketones with ammonia and amines in the presence of hydrogen is carried out on catalysts platinum oxide [957], nickel [803, 958] or Raney nickel [956, 959,960]. Yields range from low (23-35%) to very high (93%). An alternative route is the use of complex borohydrides sodium borohydride [954], lithium cyanoborohydride [955] and sodium cyanoborohydride [103] in aqueous-alcoholic solutions of pH 5-8. 

As has been described, the parent monocarbollide-metal carbonyl piano-stool species 2-(CO)n-closo-2,1 -MCB,0II n] are now known for all of the metals M = Mo (12), W (13), Re (14), Fe (11), Ru (6), Os (8), and Ni (18). Evidence also exists for a dicarbonyl-platinum analogue of compound 18,20 and as mentioned earlier, the manganese analogue of 14 has also briefly been reported.3a A notable absence from this list, however, is any representative of the Group 9 metals. The carbonyl nitrosyl-cobalt complex 21 is very closely related to the hitherto unknown dicarbonyl-cobalt dianion [2,2-(CO)2-< 7<9.v<9-2,1 -CoCB10H 11]2 and this species remains an attractive synthetic target. 

Vanhoye and coworkers [402] synthesized aldehydes by using the electrogenerated radical anion of iron pentacarbonyl to reduce iodoethane and benzyl bromide in the presence of carbon monoxide. Esters can be prepared catalytically from alkyl halides and alcohols in the presence of iron pentacarbonyl [403]. Yoshida and coworkers reduced mixtures of organic halides and iron pentacarbonyl and then introduced an electrophile to obtain carbonyl compounds [404] and converted alkyl halides into aldehydes by using iron pentacarbonyl as a catalyst [405,406]. Finally, a review by Torii [407] provides references to additional papers that deal with catalytic processes involving complexes of nickel, cobalt, iron, palladium, rhodium, platinum, chromium, molybdenum, tungsten, manganese, rhenium, tin, lead, zinc, mercury, and titanium. 

Stable five-membered dioxametallacyclic adducts are obtained from the reaction of Group VIII metal-peroxo complexes (Rh, Ir, Pd, R) with nucleophilic ketones and electrophilic alkenes or ketones. The adducts of R02(PPh3)2 with acetone and l,l-dicyano-2-methylpropene have been characterized by X-ray crystallography. The reaction of (Ph3P)2R02 with nucleophilic ketones involves, as the major pathway, the precoordination of the carbonyl compound to the vacant axial site of platinum prior to intramolecular 1,3-dipolar cycloaddition (equation 42). ... 

The hydrosilylation of carbon-heteroatom multiple bonds had received little attention until it was found in 1972 that Rh(PPh3)3Cl is an extremely effective catalyst for the hydrosilylation of carbonyl compounds. This is a new and unique reduction method since the resulting silicon-oxygen bond can easily be hydrolyzed. Other transition metal complexes including platinum, ruthenium , and rhodium also have good catalytic activity in the selective and asymmetric hydrosilylation of carbonyl compounds "". 

On the other hand, the palladium and platinum complexes of pyridine-2-aldoxime, when treated with acetyl chloride in hot chloroform, gave stable chelates containing the acylated ligand. A monoacetylated palladium chelate was isolated in which 1 mole of pyridine-2-aldoxime was replaced by two chloride ions (see reaction XXIV). This compound was identified by its infrared spectrum, which had a strong carbonyl absorption band near 1790 cm-1. The platinum complex of pyridine-2-aldoxime gave a... 

---