Dimers metal atoms

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)... 

If the reaction temperature is raised to 430 K and the carbon monoxide pressure to 3 atm, coordination of the metal atom in the rearranged product occurs via the phosphorus site, as in 159 (M = Cr, Mo, W) [84JOM(263)55]. Along with this product (M = W) at 420 K, formation of the dimer of 5-phenyl-3,4-dimethyl-2//-phosphole, 160 (the a complex), is possible as a consequence of [4 - - 2] cycloaddition reactions. Chromium hexacarbonyl in turn forms phospholido-bridged TiyP)-coordinatedcomplex 161. At 420 K in excess 2,3-dimethylbutadiene, a transformation 162 163 takes place (82JA4484). 

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. 

By use of quantitative, metal-atom, matrix-cocondensation techniques and the kinetic analysis previously discussed, the dimeric spe-... 

One of the m jor attractions in the metal-atom synthesis of dimer and cluster species is the ability to isolate highly unsaturated species, M Lm, that may then be considered to be models for chemisorption of the ligand, L, on either a bare, or a supported, metal surface (,100). It is quite informative to compare the spectral properties of these finite cluster-complexes to those of the corresponding, adsorbed surface-layers (100), in an effort to test localized-bonding aspects of chemisorption, and for deciphering UPS data and vibrational-energy-loss data for the chemisorbed state. At times, the similarities are quite striking. 

The vapor above molten Cu, Ag or Au contains predominantly atoms, but dimers are also present to ca. 0.1%. Study of these in the vapor is impeded by the high concentration of atomic metal. When these vaporized metals are cocondensed with an inert substanee, sueh as Ar, CH4, Kr, Xe at 10-12 K, a solid containing metal atoms in the inert matrix is obtained. As the proportion of metal to inert substance is... 

The structure of [Mo3S4(dmit)3] (dmit=l,3-dithiole-2-thione-4,5-dithiolate) represents one of the rare examples of M3S4 clusters where each metal atom appears as pentacoordinate instead of its more common type-I structure octahedral environment [39]. Complexes [M3Q4(dmit)3] (M = Mo, W Q = S, Se) degrade in air with an almost quantitative yield and afford a series of M(V) dimers of formula [M202(//-Q)2(dmit)2] where the oxygen atoms are in a syn configuration. 

Au-C bonds, mixed metal gold-silver dimers of planar, trinuclear complexes are readily formed by mixing gold(I) carbeniates and gold(I) benzylimidazolates with silver(I) pyrazolates in stoichiometric ratios. The complexes retain the ligands associated with the metal atoms of the starting materials. 

Salahub, D. R., 1987, Transition Metal Atoms and Dimers in Ah Initio Methods in Quantum Chemistry — II, Lawley, K. P. (ed.), Wiley, Chichester. 

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. 

Notably, dimerization of ligands was not observed when the complexes with Cu(I) salts and AgN03 were formed. Metal atoms were expected to coordinate nitrogen [Eq. (151)]. 

Let us now turn our attention to the newly emerging field of excited state metal atom chemistry. The discovery of the excited state dimerization reaction (34) ... 

These dimeric complexes involve, in their neutral state, two metal atoms in the (III) oxidation state. In the vanadium complexes such as [CpV(bdt)]2 and [CpV(tft)]2, the V—V bond length, 2.54 A in [CpV(bdt)]2, are shorter than observed in model complexes with a single V—V bond, indicating a partial double-bond character, also confirmed by a measured magnetic moment of 0.6 fiB in [CpV(tfd)]2, lower than expected if the two remaining unpaired electrons contribute to the magnetic susceptibility [20, 49]. This class of complexes most probably deserves deeper attention in order to understand their exact electronic structure. 

Hitherto no monometalated molecular pnictide exists without solvation of the main group metal atom. Therefore, the monomeric species L (Fig. 2) can only be stabilized if the Li ion has its coordination sphere enlarged through donor solvation. More importantly, the lithium phosphanides of the type K undergo oligomerization processes to form dimer, tetramer, hexamer, or polymeric assemblies M—Q (Fig. 2), which dissociate in solution more easily than related amides (2, 11, 12). 

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