Hexacoordinate centers

Pyramidal tricoordinate and tetrahedral tetracoordinate centers are centers of chirality when all substituents of the central atom are different. In contrast, penta- and hexacoordinate centers generate far more complex situations and may be elements of diastereoisomerism as well as enantiomerism. Selected cases will be considered. 

R2Sn(rV)] derivatives of N-Bz-Gly-Gly and N-Bz-Gly-Gly-Gly were found to involve both dicarboxylate binding to yield hexacoordinated Sn centers, and dimeric tetraorganodistannoxanes in which the carboxylates bind... 

Mossbauer spectroscopy has also been widely used to investigate the structures of dialkylstannylene derivatives of carbohydrates in the solid state. The usual magnitude of A = 2.78-3.07 mms indicated a coordination number larger than four, with Sn centers in a penta- or hexacoordinated environment. 

First isolated from D. desulfuricans (28), desulfoferrodoxin (Dfe) was also isolated from D. vulgaris (29). D is a 28-kDa homodimer that contains two monomeric iron centers per protein. These iron centers were extensively characterized by UV/visible, EPR, resonance Raman, and Mossbauer spectroscopies (30). The data obtained were consistent with the presence of one Dx-like center (center I) and another monomeric iron center with higher coordination number (penta or hexacoordinate), with 0/N ligands and one or two cysteine residues (center II). Comparison of known Dfx sequences led to the conclusion that only five cysteines were conserved, and that only one of them could be a ligand of center II (31). 

Fig. 12.4. Successive models of the transition state for Sharpless epoxidation. (a) the hexacoordinate Ti core with uncoordinated alkene (b) Ti with methylhydroperoxide, allyl alcohol, and ethanediol as ligands (c) monomeric catalytic center incorporating t-butylhydroperoxide as oxidant (d) monomeric catalytic center with formyl groups added (e) dimeric transition state with chiral tartrate model (E = CH = O). Reproduced from J. Am. Chem. Soc., 117, 11327 (1995), by permission of the American Chemical Society. 

With P-donors a variety of different structures are formed. Two complexes (359a,b) with a five-coordinate square pyramidal geometry and one S-donor in the apical position are reported.934,933 In a related complex (360) the nickel center reveals a distorted square planar geometry, because one xanthate ligand switched to a monodentate coordination mode. 6 By reaction of [NiL2] complexes with Ph2P(CH2)2P(Ph)(CH2)2PPh2, compound (362) is formed, which consists of a five-coordinate cation and a hexacoordinate anion. 7... 

Triply bridging carbonates between three zinc centers have been identified in nine different X-ray structures deposited in the CSD 458,461,465-467 For example, a binuclear ft-OH zinc complex with a tetradentate /V-donor ligand absorbs atmospheric carbon dioxide to a triply bridged carbonate.468 Examples are also known where the metal atoms are in varying coordination environments. The complex cation [Zn3(bipyridine)6(/U3-C03)(H20)2]4+ contains one penta- and two hexacoordinate zinc centers.469 A tetrapodal compartmental ligand forms a tetrameric complex with zinc that contains the carbonate bridging between three of the four zinc centers.470... 

Stable hypervalent silicon complexes with chelating diphosphinomethanide ligands similar to II, but with hexacoordinated silicon centers are obtained from 2 and SiCl4 (Eq.(4)). 

Hexacoordinated silicon takes benefit from the favorable octahedral arrangement of ligands around a coordination center. As expected, negatively charged substituents are superior in stabilizing high silicon coordination numbers. Most recently however, compounds with chelate ligands, mono anionic derivatives and compounds with more electropositive donors have been added to the series of penta- and hexacoordinated silicon species. 

Interaction of 137 with dimethyl sulfide in 1,2-dichloroethane leads to the formation of the polymeric adduct [137-/t6-Me2S] , which features sandwiched dimethyl sulfide molecules (Figure 22).233 The sulfur atom of the latter interacts simultaneously with the mercury centers of two neighboring molecules of 137 and thereby achieves hexacoordination. 

Polyfunctional organomercurials have emerged as useful building blocks for the construction of supramolecular species. Compound 137, for instance, was shown to complex benzene, yielding extended binary stacks where the two components alternate (Figure 25).235 These stacks are rather compact (centroid distance of 3.24 A), so that secondary 7t-interactions occur between the benzene molecule and the mercury centers. Each of the six C-C bonds of the benzene molecule interacts with one of the six mercury centers of the two juxtaposed molecules of 137. As a result, the benzene is hexacoordinated in a fashion. The strength of the Hg-C interactions must... 

A diaryldihydrosilane with a hexacoordinated silicon center, produced through intramolecular coordination, is reported not to react with benzaldehyde, although the silane is capable of reducing silver ion to silver metal.113 There is also a report of a heptacoordinate silicon hydride species with the ability to transfer hydride to trityl cation while remaining inactive toward methanol.108114... 

The triphenylmethyl-substituted germanium halide 31 can be prepared in modest yield using GeCl4 and contains a formally seven-coordinate germanium metal center (Scheme 9). The structure of 31 (Figure 2, Table 11) is a tricapped tetrahedral structure where all the three Ge-O distances are shorter than the sum of the van der Waals radii (3.62 A). A series of hypervalent germanium halides 32-34 can be prepared, as shown in Scheme 10.95 The fluoride 32 is hexacoordinate, whereas the chloride 33 and bromide 34 are pentacoordinate. 

Four of the chlorines are in the crystal lattice and bridge-bonded with neighboring titaniums, while the fifth single-bonded chlorine (Cl) protrudes from the crystal surface. The active center, which is a hexacoordinated transition metal with one vacant octahedral site, is created by replacing the single-bonded chlorine by alkylation with the alkylaluminum ... 

In terms of the development of an understanding of the reactivity patterns of inorganic complexes, the two metals which have been pivotal are platinum and cobalt. This importance is to a large part a consequence of each metal having available one or more oxidation states which are kinetically inert. Platinum is a particularly useful element of this pair because it has two kinetically inert sets of complexes (divalent and tetravalent) in addition to the complexes of platinum(O), which is a kinetically labile center. The complexes of divalent and tetravalent platinum show significant differences. Divalent platinum forms four-coordinate planar complexes which have a coordinately unsaturated 16-electron d8 platinum center, whereas tetravalent platinum is an 18-electron d6 center which is coordinately saturated in its usual hexacoordination. In terms of mechanistic interpretation one must therefore consider both associative and dissociative substitution pathways, in addition to mechanisms involving electron transfer or inner-sphere atom transfer redox processes. A number of books and articles have been written about replacement reactions in platinum complexes, and a number of these are summarized in Table 13. 

Formal octacoordination ( 4 + 4 )229 in a silicon complex was recently demonstrated by Corriu s group, who prepared 201 (equation 53). The Si-N distances (Table 27) are long relative to those common in penta- and hexacoordinate compounds, but are in the same range as those found in the heptacoordinate compounds discussed here. Also, the geometry resembles the heptacoordinate complexes, in that it is basically a tetrahedron with dimethylamino donor groups pointing toward the center, in what may be termed a tetracapped tetrahedron . 

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