Clusters chiral

The asymmetric cluster in Figure 16 is representative of the structures in which the chirality properties of the structure are not associated with any atomic site in the molecule. Metalloborane clusters with this type of symmetry properties have also been reported. The stereochemical notation for asymmetric clusters will have to specify cluster chirality. And when clusters with more complex ligand substitution patterns and chiral ligands are prepared, the configurations of all metal centers and the chiralities of the associated ligands must be given. 

A number of review articles have described the applications of multinuclear NMR methods for studying structures and internal rearrangements of metal clusters. The more specific cluster types covered were transition metal carbonyl clusters/ chiral clusters/ and mixed metal clusters containing carbyne or ketenylidene bridges. ... 

Isopropyl group (Section 2 13) The group (CH3)2CH— Isotactic polymer (Section 7 15) A stereoregular polymer in which the substituent at each successive chirality center is on the same side of the zigzag carbon chain Isotopic cluster (Section 13 22) In mass spectrometry a group of peaks that differ in m/z because they incorporate differ ent isotopes of their component elements lUPAC nomenclature (Section 2 11) The most widely used method of naming organic compounds It uses a set of rules proposed and periodically revised by the International Union of Pure and Applied Chemistry... 

Fig. 1. Typical ED pattern of polychiral MWCNT. The pattern is the superposition of the diffraction patterns produced by several isochiral clusters of tubes with different chiral angles. Note the row of sharp oo.l reflexions and the streaked appearance of 10.0 and 11.0 type reflexions. The direction of beam incidence is approximately normal to the tube axis. The pattern exhibits 2mm planar symmetry [9].

The diffraction patterns due to different isochiral clusters are superimposed and well separated in a polychiral MWCNT diffraction pattern, suggesting that interference between waves scattered by tubes with different chiral angles can be neglected. It is therefore meaningful to discuss only isochiral clusters of tubes. Such clusters are only compatible with a constant intercylinder spacing c/2 for pairs of Hamada indices satisfying the condition = L +M +LM - (nc/a). Approximate solutions are for instance (8, 1) and (5, 5) [16,17]. 

The diffraction patterns of isochiral clusters of tubes with different chiral angles in MWCNTs are superimposed in the composite pattern, the different chiral angles can be measured separately by diffraction contrast imaging [26]. 

The problem that we noted above with clusters appears also in chemical enumeration when we consider compounds formed by attaching radicals which may be chiral or achiral to a frame which is achiral. In this case, too, Polya s Theorem cannot be used, but the problem can be solved by the appropriate use of Burnside s Lemma. It is also amenable to the methods of Redfield, as shown in [DavRSl] and [LloE85]. 

An unprecedented stereoselective procedure to obtain enantiomerically pure transition cluster M3Q4 complexes consists of the direct excision of the M3Q7X4 n polymers using chiral diphosphanes, namely (+)-l,2-bis[(2J ,5R)-2,5-(dimethylphospholano)]ethane [(R,R)-Me-BPE] and its respective enantiomer [(S,S)-Me-BPE] to afford the trinuclear complexes (P)-[Mo3S4Cl3(J ,J -Me-BPE)3] and (Af)-[Mo3S4Cl3(S,S-Me-BPE)3] , respectively [30]. The structures of both enantiomers are shown in Fig. 7.3. The symbols (P) and (M) refer to the rotation of the chlorine atoms around the C3 axis, with the capping sulfur pointing towards the viewer. 

Circular dichroism (CD) is another interesting example of an optical property of the small Au SR clusters. Since the first observation of Schaaff et al. [23,24], several reports have appeared regarding the CD activities of gold clusters protected by chiral thiols such as penicillamine [25] and A-isobutyryl-cysteine [26]. Figure 11 shows the CD spectra of 1-9, which is a good reproduction of the original report by Whetten s group [23,24]. 

The Au SG clusters were optically active in the visible and UV spectral range, with the anisotropy factors in the order of several tens to hundred parts per million. The origin of the observed optical activity in core-based electronic transitions has been previously discussed [24]. The key question is whether the gold cluster is intrinsically chiral or whether the optical activity is induced by the chiral ligation environment. The first possibility has been supported by theoretical studies performed by Garzon and... 

The 29Si resonance is therefore a single narrow line. However for dialkylpolysilanes with two different alkyl groups on each silicon, (RR Si)n, each silicon atom is a chiral center and the resonance for a particular silicon will depend upon the relative stereochemistry of other nearby silicon atoms. For such polymers, a rather symmetrical cluster of peaks is observed (Figure 5). These results are consistent with atactic structures, having a statistical (Bernoullian) distribution of relative configurations.(32,33)... 

Complex clusters incorporating multiple-bridging groups such as O2-, CC1, and CC02 have been known for some time, with clear synthetic routes available.86 Typical species include 03-CCl)Co3(CO)9, (//3-CC02)Co3(CO)9, and Co4(/x4-0)[(/i3-CC02)Co3(CO)9]6. Substitution of further carbonyls can lead to chiral clusters. 

A particularly elegant example of cluster formation involving chiral recognition and retention of chirality through an increasingly complex hierarchical series of clusters is that of rubrene on Au l 1 1 [9] illustrated in Figure 1.5... 

Figure 1.5 (a) Hierarchy of clusters of rubrene on Au l 1 1, showing the evolution from trimers to pentamers of trimers and eventually 150 molecules per cluster as a decamer of the pentamers. (b) Illustration ofthe preservation of chirality through the hierarchy. (Adapted with permission from Ref. [9]). 

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