Zinc centers

When the phosphonium ylide 81 is reacted with zinc amide, the corresponding a-zincated phosphorus yUde is formed. Thermally unstable, it evolves almost quantitatively to zincatacyclobutane 82 which in presence of pyridine leads to the formation of the zincataphosphoniaindane 83. In order to explain this unprecedented cyclometallation reaction, a mechanism is proposed involving a low coordinated zinc center. The new product, reacted with benzaldehyde leads to the diphenylallene 84 (Scheme 27) [106-108]. 

Figure 17.8 Catal3ftic zinc center of horse liver alcohol dehydrogenase revealed from an X-ray crystallographic structure (PDB file 20HX) [Al-Karadaghi et al., 1994]. The bound NADH cofactor, a molecule of the inhibitor dimethylsulfoxide (DMSO), and the amino acid residues that coordinate the Zn are shown as sticks shaded according to the elements, and the Zn center is shown as a gray sphere, while the protein is shown in thin gray lines.

The structures of [TpMe2]2Zn (80) and [Tpph]2Zn (85) have been determined by x-ray diffraction (Fig. 28). Interestingly, [TpMe2]2Zn and [TpPh]2Zn do not possess similar structures. Specifically, whereas the zinc center in [TpMe2]2Zn is six-coordinate and octahedral, the zinc center in [TpPh]2Zn is only four-coordinate and tetrahedral. Thus, the potentially tridentate [TpPh] ligand acts only as a bidentate ligand in [i72-TpPh]2Zn. However, it should be noted that the Fe in the related complex [TpPh]2Fe is octahedrally coordinated (90). 

X-ray diffraction studies on several forms of the enzyme have demonstrated that the active site is composed of a pseudo-tetrahedral zinc center coordinated to three histidine imidazole groups and either a water molecule [(His)3Zn-OH2]2+ (His = histidine), or a hydroxide anion [(His)3Zn-OH] +, depending upon pH (156,157). On the basis of mechanistic studies, a number of details of the catalytic cycle for carbonic anhydrase have been elucidated, as summarized in Scheme 22... 

X-ray diffraction studies on [TpBut,Me]Zn 2(/i,-r)1,Tj1-C03) have identified that the bridging carbonate ligand is coordinated to each zinc center in a unidentate fashion (171,172), which thereby provides additional support for the presence of a unidentate, rather than bidentate, bicarbonate ligand in [TpBut,Me]Zn(0C02H). The carbonate complex [TpBut,Me]Zn 2(/iA-7)1,T)1-C03) is also characterized by v(CO) absorptions at 1587 and 1311 cm-1 in the IR spectrum (173), and a 13C NMR signal at 8 164 ppm (in C6D6). 

Secondly, the molecular structure of [TpPr 2]Zn 2(/u,-7)1,7)2-C03), as determined by x-ray diffraction (151,153), reveals that the carbonate ligand is coordinated in an asymmetric manner, with unidentate coordination to one zinc center and bidentate coordination to the other zinc center, i.e., fi-ri1,ri2-C03 (Scheme 24). Such coordination is noticeably distinct from that of [TpBut Me]Zn 2(/x.-r)1,7 1-C03), in which the carbonate ligand bridges in a symmetric unidentate mode. 

The Zn-0 distance is 2.8 A, indicating a relatively weak association. Moreover, the nitrate ligand does not displace the coordinated water from the zinc center. See Mangani, S. H kansson, K. Eur. J. Biochem. 1992, 210, 867. 

Smith (91) reported an X-ray crystal structure of a zinc porphyrin polymer (77, Fig. 32) where, unusually, the coordination bond is between a nitro group and the zinc center. The tetranitroporphyrin is highly substituted, and the resulting steric hindrance causes the macrocycle to be noticeably distorted. Adjacent porphyrin planes in the polymer are almost orthogonal. However, there is no evidence of polymerization in solution, and the nitro-zinc interaction is probably too weak to maintain this structure outside the solid state. 

Zinc complexes of a fused pyrroloporphyrin, cyclopropanochlorin, that contain an appended isocyano group show dimer formation. The X-ray structure reveals five-coordinate zinc centers... 

A zinc-mediated carbon-carbon coupling reaction can be carried out on the metallated form of (t-butyldimethylsilyl)(2-pyridylmethyl)amine, formed in reaction with dimethylzinc. The isolated dimeric species can be reacted with further dimethyl zinc to give bis(methylzinc)-l,2-dipyridyl-l,2-bis(t-butyldimethylsilylamido)ethane, which contains two N3C coordinated zinc centers.89... 

The ligand 2,5-bis(2-pyridyl)pyrazine was used in the synthesis of a range of zinc compounds to contrast with copper coordination polymers prepared with this ligand.169 Three zinc compounds were structurally characterized, [ZnCl2L(DMF)], [Zn3(OAc)6L2], and [Zn3Cl6L3] respectively a distorted square planar monomer, a linear trimer, and a triangular arrangement of zinc centers. 

EXAFS has been used to determine the second hydration shell of zinc in aqueous solution. Aqueous solutions of zinc nitrate over a range of concentrations were examined and a Zn—O distance of 2.05 A for the first shell of the six-coordinate zinc center found, which is unaffected by concentration. The second hydration shell shows a Zn—O distance which has no systematic trend but an average distance of 4.1 A. The coordination number for the second shell is 11.6 1.6 with unusual behavior for the most concentrated 2.7 M solution, which has a decrease in coordination number to 6.8 1.5 340... 

There are a reasonable number of structurally characterized zinc compounds with bound THF molecules. For example, a six-coordinate zinc porphyrin complex with axial THF donors and a four-coordinate zinc center with two THF ligands and two phenolate ligands.341,357 Although less common there are other structural examples of ether solvents, such as diethyl ether, coordinated.358 The X-ray structure of zinc chloride with 1,4-dioxane ligands shows a monomeric four-coordinate zinc center with two 1,4-dioxane ligands.359... 

Zinc squarate (C4O42 ) can form a solid state compound with a layered structure when DMSO is present, [Zn(C404)(OH2)2(DMSO)2]. The DMSO occupies the axial positions at the six-coordinate zinc center and prevents formation of a 3D cage network. The compounds are insoluble at room temperature but are converted into the 3D cage network [Zn(C404)(0H2)2] by heating in aqueous media.385... 

The compound Zn2(diacetoamidoglutarate)2hexaaquo is dimeric with two slightly distorted trigonal-bipyramidal zinc centers. The A-protected amino acids bridge the two zinc centers,... 

The crystal structure of zinc phenylphosphonate was solved and demonstrated the anticipated layer structure with the phenyl rings occupying the interlamellar space.409 The structure of zinc ethylphosphonate and (2-aminoethyl)phosphonate both show four-coordinate zinc centers in contrast to the coordination number of six in the phenylphosphonate compound.410... 

The presence of triethylenetetramine in the hydrothermal synthesis of open-framework zinc phosphates results in a number of frameworks with one- to three-dimensional structures. The structures include one-dimensional ladders, two-dimensional layer structures, and one structure where the tetramine is bound to the zinc center. The structural type was highly sensitive to the relative concentration of the amine and phosphoric acid.411 Piperazine and 2-methylpiperazine can be used as templating molecules in solvothermal syntheses of zinc phosphates. The crystallization processes of the zinc compounds were investigated by real time in situ measurements of synchrotron X-ray powder diffraction patterns.412... 

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