Platinum carbonylation

Advances in platinum metal carbonyls and their substituted derivatives, II. Rhodium, iridium, palladium and platinum carbonyls. S. C. Tripathi, S, C. Srivastava, R. P. Mani and A. K. Shirma), Inorg. Chim. Acta, 1976, 17, 257-290 (463). 

Phosphine palladium and phosphine platinum carbonyl cluster compounds. N. K. Eremenko, E. G. Mednikov and S. S. Kurasov, Russ. Chem. Rev. (Engl Transl.), 1985, 54, 394 (69). 

Large platinum carbonyl clusters have been investigated as models for the adsorption of carbon monoxide on platinum surfaces and on platinum electrodes. An issue is how large the clusters must be before they adopt the properties of the bulk metal. Teo et al. have investigated the magnetic properties of the clusters [Pt6(CO)12]2+, [Pt9(CO)18]2+, [Pt y(CO)22f+, and... 

Bischoff, H., )aeger, N.I., Sdiultz-EHoff, G., and Kubelkova, L (1993) Interaction of CO with platinum spedes in zeolites. Evidence for platinum carbonyls in partially reduced zeolite PtNaX. J. Mol Catal, 80,... 

Platinum carbonylate anion clusters like [Pt3(CO)6] can be obtained by alkaline reduction of [PtCh] in a CO atmosphere. From [Pt3(CO)s] other higher nuclear-ity anions can be obtained. In this context, several examples have been reported in which this type of anionic cluster is used in the preparation of catalysts by impregnation or exchange methods. Salts of [Pt3 (CO)6 ] (n = 3, 5) have been used to prepare, by impregnation, dispersed platinum on ZnO and MgO [49] and, by ion exchange methods, to prepare Pt3 /C electrodes for the electrocatalytic oxidation of methanol [50]. A salt of [Pti2(CO)24] has recently been used to prepare... 

Other works related to the use of platinum carbonyl species in the preparation of catalysts, which lie beyond the scope of this chapter, refer to the synthesis in situ of supported platinum carbonylate species. For this purpose, the impregnation or exchanging of Pt precursors as [Pt(NH3)4], [Ptcy and [PtCLt] " on an appropriate support is carried out. Then, the carbonylation renders a carbonylate species that could be naked to metal frameworks by appropriate decarbonylation. 

Scheme 16.14 Convenient syntheses of platinum carbonyl compounds on the surface of Si02 (under 1 atm CO at 25°C).

The [Pt6(CO)12]2- dianion can be used as starting material for the synthesis of other platinum carbonyl cluster complexes.1,3... 

X-ray diffraction studies on salts of the nickel and platinum carbonyl dianions [M3(CO)3(m2-CO)3] 2 (M = Ni, Pt) showed that these... 

This section on platinum carbonyl complexes should be read in conjunction with the comparable chapter by Hartley in Comprehensive Organometallic Chemistry , Volume 6, Chapter 39. This section will emphasize very recent work and will omit compounds which are completely organometallic in nature. 

Heterometallic metallomesogens, liquid crystals, 12, 223—224 Heterometallic polynuclear platinum carbonyl complexes heterodinuclear clusters, 8, 415 triangular clusters, 8, 417... 

Homoleptic platinum carbonyl anions, characteristics, 8, 410 Homoleptic tantalum complexes, preparation and characteristics, 5, 108... 

Iron-platinum carbonyl clusters, characteristics, 8, 415 Iron reagents, in Kumada-Tamao-Corriu reaction, 11, 21 Iron-rhodium clusters, as heterogeneous catalyst precursors,... 

We were able to prepare (63) iron carbonyl halides of lower carbon monoxide content, Fe(CO)2X2, which are formally related to the long-known platinum carbonyl compounds (62), e.g.,... 

The so-called platinum carbonyl readily reacts further with alkali, dissolving to give a series of dianions with general formula [Pt3(CO)6]n2- (n = 6, 5, 4, 3, 2). Each of these dianions can be obtained in a pure state by careful control of the initial OH /Pt(IV) ratio (n = 3, OH-/Pt = 8-9 n = 4, OH-/Pt = 6-6.1 n = 5, OH /Pt = 5.7). However, these ratios are quite critical and the reaction must be followed by IR. If the incorrect product is formed, the desired final product can be obtained by adding further small amounts of alkali or of sodium hexachloroplatinate. 

Carbomethoxylation of olefins toa, -unsaturated esters or (3 -methoxy-esters (Eq. (127) can be achieved if the electrolysis in CH3OH/NaOCH3 at platinum electrodes is conducted under CO pressure. A platinum carbonyl-complex Ptx (CO)y is assumed to be the reactive intermediate in this synthetically interesting reaction 289 ... 

Cluster Compounds.—An interesting new series of platinum carbonyl dianions of formula [Pt3(CO)3(p2-CO)3]2 n = 2—5) have been synthesized by reduction of [PtClg]2" with CO and methanolic NaOH.107 Species with decreasing n were isolated with increasing concentration of reducing agent (equation 18). The X-ray... 

Fukuoka, A., Higashimoto, N., Sakamoto, Y., Sasaki, M., Sugimoto, N., Inagaki, S., Fukushima, Y. and Ichikawa, M. Ship-in-bottle synthesis and catalytic performances of platinum carbonyl clusters, nanowires, and nanoparticles in microporous and mesoporous materials, Catal. Today, 2001, 66, 23-31. 

Carbon monoxide has been found to be surprisingly reactive toward the metals in Group VIII, in both their oxidized and unoxidized states. A sizable number of compounds exist in which one or more CO molecules are attached to a metal atom through the carbon typical of these are nickel tetracarbonyl, Ni(CO)4, iron pentacarbonyl, Fe(CO) cobalt carbonyl hydride, Co(CO)4H platinum carbonyl chloride, Pt(CO)2Cl2 and more complicated molecules such as Co4(CO)i2. 

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