Rhodium clusters reaction with

The dominant role of copper catalysts has been challenged by the introduction of powerful group VIII metal catalysts. From a systematic screening, palladium(II) and rhodium(II) derivatives, especially the respective carboxylates62)63)64-, have emerged as catalysts of choice. In addition, rhodium and ruthenium carbonyl clusters, Rh COJjg 65> and Ru3(CO)12 e6), seem to work well. Tables 3 and 4 present a comparison of the efficiency of different catalysts in cyclopropanation reactions with ethyl diazoacetate under standardized conditions. 

Niobium and rhodium cluster anions have been prepared by laser vaporization and the reactions with benzene studied by FT-ICR/MS (58). The reactions of the anions and similar cations have been compared. With few exceptions the predominant reaction of the niobium cluster anions and cations was the total dehydrogenation of benzene to form the metal carbide cluster, [Nb C6]-. The Nb19 species, both anion and cation, reacted with benzene to form the coordinated species Nb 9C6I I6p as the predominant product ion. The Nb22 ions also formed some of the addition complex but the Nb2o Nb2i, and all the other higher clusters, formed the carbide ions, Nb C6. ... 

The incorporation of bridging germanium ligands into high-nuclearity transition metal clusters has been accom-plished. Thermal reaction of Ph3GeH with rhodium carbonyl yields a mixture of germanium/rhodium cluster... 

Rearrangements of clusters, i.e. changes of cluster shape and increase and decrease of the number of cluster metal atoms, have already been mentioned with pyrolysis reactions and heterometallic cluster synthesis in chapter 2.4. Furthermore, cluster rearrangements can occur under conditions which are similar to those used to form simple clusters, e.g. simple redox reactions interconvert four to fifteen atom rhodium clusters (12,14, 280). Hard-base-induced disproportionation reactions lead to many atom clusters of rhenium (17), ruthenium and osmium (233), iron (108), rhodium (22, 88, 277), and iridium (28). And the interaction of metal carbonyl anions and clusters produces bigger clusters of iron (102, 367), ruthenium, and osmium (249). 

The chemistry of the carbidocarbonyl clusters of cobalt and rhodium (none is known for iridium) is predominantly the work of Italian school of the late Paolo Chini and colleagues. The first rhodium cluster of this type to be reported was [Rh6C(CO)ls]2, 24 (59), isolated as a minor by-product in the synthesis of [Rh7(CO)t6]3- (and originally misformulated as [Rh3(CO)l0]-). The formation of 24 resulted from the reaction of [Rh7(CO)l6]3- with chloroform (the source of the carbon atom), present as an impurity in the reaction solvent, and 24 is now synthesized by this reaction [Eq. (17)]. 

Halocarbons have been used successfully as a source of carbide atoms in the synthesis of carbido clusters of rhodium and nickel. For example, [RhgCCCO) ] may be synthesized by the reduction of Rh4(CO)i2 with alkali hydroxide in methanol followed by reaction with chloroform 184), or by the reaction of [Rh(CO)4] with CCI4 according to Eq. (1). 

A few homometallic HNCC have also been produced by the condensation reactions of anionic carbonyl clusters with cationic complexes. For instance, sequential buildup of rhodium HNCC via incorporation of Rh(CO)2 fragments has been achieved by reacting [Rh(CO)2(MeCN)2] in acetonitrile with a series of anionic rhodium clusters as illustrated by the reactions shown in Eqs. (11) and (12) (223). 

The reduction of neutral carbonyls with alkali metal hydroxides or carbonates is an important route to HNCC dianions. In a few instances reduction of rhodium clusters has been reported to proceed further with oxidation of another CO. Examples are the formation of [Rh6(CO)i4] from [Rh6(CO)i5] 170) (Scheme 16) and the reduction of the dicarbide [Rhi2(C)2(CO)24] to give [Rhi2(C)2C023] 213). In the latter case, the unstable paramagnetic intermediate [Rh 12(0)2(00)23] has also been isolated upon slight alteration of the reaction conditions [Eqs. (32) and (33)]. 

In rhodium clusters, e.g., [Rh13(CO)14H5. ]" (n = 2 and 3), only one of the H atoms is encapsulated and 3H nmr spectra show that this atom interacts with all 13 Rh atoms (103Rh, spin V2) and is thus migrating within the cluster. Proton transfer reactions of interstitial hydrides have been studied72 and more complex hetero-nuclear species73 can be made by reactions such as... 

There are few reports of reactions between alkynes and trinuclear clusters of metals other than iron, ruthenium, or osmium. Some rhodium, platinum, and mixed-metal clusters undergo metal-metal bond rupture in reactions with alkynes (54-56), while in other cases the alkyne coordinates to the trinuclear unit without causing any major changes in framework geometry (56-59), as illustrated in Eq. (3). 

The reaction of M3(CO)12 with both open-chain and cyclic poly-alkenes has attracted some attention, especially in the case of Ru3(CO)i2. In most of the examples reported, the organic fragment bonds to the metal framework in such a way as to interact with more than one of the three metal atoms (68-77). There are some exceptions to this general statement, however. One is the reaction of Ru3(CO)j 2 with cyclopentadiene, in which a mononuclear complex is obtained (78). In other cases, tetranuclear and hexanuclear compounds are obtained (79 81). Cluster breakdown has also been observed in the case of a rhodium complex upon reaction with ethylene (55) as shown in Fig. 3. 

The hexanuclear carbonyl Rh6(CO)ie was first prepared by treating anhydrous rhodium trichloride with carbon monoxide at 200 atm for several hours in the presence of a halogen acceptor such as cadmium, copper powder, silver, or zinc at temperatures of 80-230°.i At temperatures of 50-80°, the main product was Rh4(CO)i2. Optimum yields (80-90 %) of Rh6(CO)i6 are obtained by allowing methanolic solutions of rhodium trichloride trihydrate to react with carbon monoxide at 40 atm and 60°. Recently, however, there have been reports - of new high-yield syntheses of rhodium cluster carbonyls which require only ambient pressures of carbon monoxide. Chini and Martinengo have obtained Rh6(CO)i6 and Rh4(CO)i2 in high yield from the reaction of Rh2(CO)4Cl2 with carbon monoxide at atmospheric pressure and room temperature. 

The initial observation of remarkable size-dependent reactions of deuterium with clusters of cobalt and niobium was rapidly followed by other reports of dihydrogen addition reactions with clusters of many metals, in some cases containing more than 100 atoms. Further work was reported for nio-bium " and cobalt as well as for iron, vanadium, " nickel, platinum, rhodium, tantalum, and aluminum. ... 

Niobium and cobalt clusters exhibit size-sensitive reactions with nitrogen with a reactivity pattern similar to that observed for hydrogen. The reactivity of rhodium clusters (n = 1-12) toward N2 has also been studied. In this case the atoms through the tetramer appear to be inert, with reactivity turning on at Rhj. Maximum reactivity occurs at Rh7, and subsequently drops off by roughly a factor of 2 in going from Rh, to Rh,. Iron clusters appear to be nearly unreactive toward N2. Attempts to induce low-pressure ammonia synthesis on gas-phase iron clusters indicate that hydrogenated iron clusters Fe H are also unreactive toward N2. ... 

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