Metal dimer

Two elasses of systems illustrate eases for whieh heterolytie bond dissoeiation lies lower than the homolytie produets. The first involves transition metal dimer eations, M2. Espeeially for metals to the right side of the periodie table, sueh eations ean be eonsidered to have ground-state eleetron eonfigurations with a d d +i eharaeter, where the d eleetrons are not heavily involved in the bonding and the a bond is formed primarily from the metal atom s orbitals. If the a bond is homolytieally broken, one forms X + Y = M (s d +i)... 

M(0H)2SOi, H2O where M=Zr (8), Hf (12) also have been determined and reveal the presence of almost planar zigzag chains of metal atoms joined by double hydroxide bridges. The single exception to this trend toward formation of double hydroxy-bridged metal dimers or chains is the compound which is best described as CeOSOif,H20 (17). However, even in this structure the cerium ions form chains which are linked by bridging oxide ions. 

We have already shown how simultaneous codeposition of two metals in inert-gas matrices can lead to the formation of mixed-metal dimers. As in the case of silver, it was found that irradiation into the atomic absorptions of Cr or Mo results in formation of their respective dimers and trimers (114). In addition to this, however, irradiation into the atomic resonances of the two metals in the presence of each other results (114) in formation of the mixed-metal species CrMo, CrjMo, and CrMo2. It would seem that selective irradiation into the 300-400-nm bands of atomic Cr or Mo excites the 3d 4p, 3dMs 4p , or 4d 5p, ... 

In an earlier work, we have proposed a theoretical procedure for the spectroscopy of antiferromagnetically (AF) coupled transition-metal dimers and have successfully applied this approach to the electronic absorption spectrum of model 2-Fe ferredoxin. In this work we apply this same procedure to the [Fe2in - 82) P o - CeH48)2)2 complex in order to better understand the electronic structure of this compound. As in our previous work" we base our analysis on the Intermediate Neglect of the Differential Overlap model parameterized for spectroscopy (INDO/S), utilizing a procedure outlined in detail in Reference 4. 

Saue, T. and Jensen, H.J.Aa. (2003) Linear response at the 4-component relativistic level Application to the frequency-dependent dipole polarizabilities of the coinage metal dimers. Journal of Chemical Physics, 118, 522-536. 

Ortiz, G. and Ballone, P. (1991) Metastability of doubly charged transition-metal dimers in density-functional theory. Physical Review B -Condensed Matter, 44, 5881-5884. 

The hydrolysis of p-nitrophenyl acetate and bis(p-nitrophenyl phosphate) are frequently used to probe hydrolytic activity. A problem with some other dinuclear systems is that the Zn units are held together by bridging ligands which can be cleaved on reaction with the substrate.440 This is not the case in a ditopic ligand such as those designed by Lippard and co-workers based on Kemp s triacid imide with a xylyl spacer.441,442 Both zinc dimers and mixed metal dimers were formed and a structure characterized with a bridging phosphodiester (Figure 6). 

Thus, the SCF-Xa-SW calculations for the metal dimers confirm the anomaly of the technetium clusters that was experimentally observed in previous studies [9-11], It should be noted that because the actual structure of the... 

All three of the mixed-metal dimers react with CO to give the respective dicarbonyl compounds, CpM(CO)2 (M = Co, Rh, RuH), and (tj-C5Me5)2Zr(CO)2 (30). It is presumed that this reaction is initiated by the breaking of the zirconium-/x-i71,T)2-carbonyl bond. 

In the last example, a serious handicap is the extreme sensitivity of the calculations to the parameterization of the metal atoms. In a paper concerning the spin states of metal dimer complexes (38) as studied by EHT, heavy manipulation of the original theory was needed. In the field of transition metal coordination compounds self-consistent charge (SCC) calculations (of the type already mentioned for electronegative atoms) are essential to obtain the diagonal elements Hu. 

Reduction of the metal dimer [CpMo(NO)l2]2 with Na/Hg in the presence of a variety of acyclic dienes generates the (diene)MoCp(NO) complexes in moderate to low isolated yield (equation 8)12,31,89. For the majority of diene ligands, complexes 60 are formed exclusively as the s-trans isomers as evidenced by NMR spectroscopy and single-crystal X-ray diffraction analysis. In comparison, complexation of the 2,3-dimethyl-l,3-butadiene initially gives a separable mixture of the s-trans (60) and s-d.v-complex (61). The s-cis isomer isomerizes to the more thermodynamically stable s-trans isomer in solution (THF, 1/2 = 5 min C6H6, ti/2 = 24 h). 

The reaction of a metal-dimer with H2 can also be regarded as an oxidative addition reaction. For instance, a dimer of a d7 metal complex reacts with dihydrogen to give two d6 species. In this process dihydrogen also gives formally two hydride anions. A well-known example in the present context is the conversion of dicobaltoctacarbonyl into hydridocobalttetracarbonyl ... 

In approaching the design of a chiral catalyst, the first question was whether or not our computational approach would allow prediction of the conformation of the ligands around the Rh-Rh core. Although several hundred tetrakiscarboxylato metal-metal dimers were known [20], there had been no report of a dicarboxylic acid that would bridge two positions on such a dimer [21]. We reasoned that the best chance for success would be with a dicarboxyhc acid that was specifically designed to fit across the 5.4 A gap between the carboxylate Hgands. 

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