Sandwich-type complexes

ELISA utilizes complex ( sandwich-type ) and highly specific interactions between immobilized antibody and antigen (microorganism) present... 

CyclooctatetraenylCompounds. Sandwich-type complexes of cyclooctatetraene (COT), CgH g, are well known. The chemistry of thorium—COT complexes is similar to that of its Cp analogues in steric number and electronic configurations. Thorocene [12702-09-9], COT2Th, (16), the simplest of the COT derivatives, has been prepared by the interaction of ThCl [10026-08-1] and two equivalents of K CgHg. Thorocene derivatives with alkyl-, sdyl-, and aryl-substituted COT ligands have also been described. These compounds are thermally stable, air-sensitive, and appear to have substantial ionic character. 

SCHEME 3 The electrochemical gene sensing system based on the formation of complementary sandwich-type complex, (a) Target DNA combines the ferrocenyl ODN with the probe ODN on the electrode. Redox currents due to the surface-confined ferrocenyl units should reflect the concentration of the target, (b) Ferrocenyl units are not deposited onto the electrode using nontarget DNA. 

The coordinated ligand is called rj6-boratabenzene by Chemical Abstracts however, as ligands in sandwich-type complexes should be named as neutral entities according to the IUPAC rules, Tj6-bora-3,5-cyclo-hexadien-2-yl would be the correct name. For the sake of simplicity we prefer boratabenzene in the following. 

Boron resonances (Table III) appear in the range expected for sandwich-type complexes with metal-boron bonding (for reference data see Ref. 50). In cases where pairs of B-methyl and B-phenyl derivatives (as, e.g., 9 and 17) are known, the nB resonance of the methyl compound is at lower field by 2.0-3.7 ppm (average, 2.6 ppm). 

Simple transition metal halides react cleanly with alkali metal boratabenzenes. In this way sandwich-type complexes 32 of V (27), Cr (64), Fe (58), Ru (61), and Os (61) have been made. The corresponding nickel complexes seem to be nonexistent, quite in contrast to NiCp2 in attempted preparations, mixtures of diamagnetic C—C linked dimers were obtained (29). In the manganese case, high sensitivity to air and water has precluded preparative success until now. Some organometallic halides have added further variations to the main theme. The complexes 33 of Rh and 34 of Pt were obtained from [(COD)RhCl]2 and [Me3PtI]4, respectively (61). 

The discovery in 1951 of the transition metal rr-complex, ferrocene or bis-cyclopentadienyl-iron, Fe(Cp)2, (1, 2) led to enormous interest being shown in the possible structures of such compounds and in the nature of the metal-ring bonding. Within a year the sandwich type structure (Fig. 1) had been proposed (2), and an outline treatment of the metal 3d-ligand 7r-orbital interaction by Jaffe (4) was soon followed by a more detailed molecular... 

Coordination compounds composed of tetrapyrrole macrocyclic ligands encompassing a large metal ion in a sandwich-like fashion have been known since 1936 when Linstead and co-workers (67) reported the first synthesis of Sn(IV) bis(phthalocyanine). Numerous homoleptic and heteroleptic sandwich-type or double-decker metal complexes with phthalocyanines (68-70) and porphyrins (71-75) have been studied and structurally characterized. The electrochromic properties of the lanthanide pc sandwich complexes (76) have been investigated and the stable radical bis(phthalocyaninato)lutetium has been found to be the first example of an intrinsic molecular semiconductor (77). In contrast to the wealth of literature describing porphyrin and pc sandwich complexes, re-... 

Crown ethers whose cavity is too small to accommodate the anion overcome this handicap in an ingenious way by forming sandwich-type complexes (5). The formation of 2 1 complexes is very sensitive to steric... 

Several half-sandwich-type derivatives, in which the allenylidene unit is generated from propargylic alcohols following the Selegue s protocol, are known. Representative examples include (1) the cationic cyclopentadienyl complexes [CpOs (=C=C=CPh2)(L )(L )][PF6] (L = = PPhs, Pi-Prs = Pi-Prs, = CO,... 

In accord with the expected trans influence of the 71-acceptor aUenylidene unit [212], substitution of the chloride ligand by different anionic nucleophiles in complexes frans-[MCl(=C=C=CR R )(Pi-Pr3)2] (M = Rh, Ir) is favored, affording new aUenylidene derivatives frans-[MX(=C=C=CR R )(P/-Pr3)2] (X = I, F, OH, N3, etc.) (see reactivity studies below). Of particular interest is the behavior of the Rh(I) species frans-[RhCl(=C=C=CPh2)L2] (L = Pf-Pr3, f-Pr2AsCH2CH20Me) towards NaCsHs since the reactions lead to the clean formation of complexes 40 (Scheme 13), the only half-sandwich-type Group 9 allenylidenes presently known [206, 209]. 

The medium-ring cyclic triamines, 1,4,7-triazacyclononane (tacn), 1,4,7-triazacyclodecane (tacd), 1,4,8-triazacycloundecane (tacud), and 1,5,9-triaza-cyclododecane (tacdd) have been synthesized and the cobalt complexes [Co(tacn)2]Br3, [Co(tacd)2]Br3,H20 and [Co(tacud)BrCl2] isolated. It has been suggested that the structures are of the sandwich type [viz. (95) and (96) "] and, for this reason, the reporter looks forward to publication of X-ray structural analyses. 

The following conclusion of the theory (1 ) is extremely important. The radiative transition 2 > Sq in a sandwich dimer is forbidden. In case of a dimer of 04 symmetry, the transition 2 (4Eg) > Sg (A g) is forbidden because of parity. There is no principle difference in the splitting nature of 2 and states for sandwich type dimers with lesser than D4h symmetry and the 2 > Sq transition remains quasi forbidden. This makes it possible to explain low P2 values obtained in (1 ) by a decrease of the 2 > Sg transition radiative probability, i.e., by decreasing or 2 > Sq fluorescence quantum yield in dimeric TTA complexes. In the case of non-sandwich dimer structures with location of subunits in one plane, the So state also is split into two states (high 202y and low 2B3g). However, two radiative transitions S2(B2y)... 

The nature and extent of /-orbital participation in the bonding of uranocene and other bis(cyclooctatetraenyl) actinides has never been satisfactorily established, although a good deal of effort has been expended on it. The X-ray structures do not resolve the issue because an ionically bonded model would also lead to a sandwich-type structure (for example, MgCp2 has essentially the same structure as ferrocene). Other physical techniques have been used, but the complexity of the electronic structures often leads to ambiguous interpretations. 

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