Apical positions

The most important members of this class are the osmium nitrido, and the osmyl complexes. The reddish-purple K2[OsNCl5] mentioned above is the result of reducing the osmiamate. The anion has a distorted octahedral structure with a formal triple bond Os=N (161pm) and a pronounced /ram-influence (pp. 1163-4), i.e. the Os-Cl distance trans to Os-N is much longer than the Os-Cl distances cis to Os-N (261 and 236 pm respectively). The anion [OsNCls] also shows a rram-effect in that the Cl opposite the N is more labile than the others, leading, for instance, to the formation of [Os NCl4] , which has a square-pyramidal structure with the N occupying the apical position. 

The assumed transition state for this reaction is shown in Scheme 5.5. The two bulky t-butoxy groups are expected to locate at the two apical positions. One of the 3,3 -phenyl groups would effectively shield one face of an imine, and consequently, a diene attacks from the opposite side. Judging from this model, similar selectivities were expected in the Mannich-type reactions of imines with silyl eno-lates. Actually, when ligand 10 was used in the reaction of imine la with S-ethyl-thio-l-trimethylsiloxyethene, the corresponding / -amino thioester was obtained in 84% ee (Scheme 5.6). As expected, the sense of the chiral induction in this case was the reverse of that observed when using catalyst 6 [12, 25]. 

The structures of several adducts can be rationalized on the basis [128] that in a 5-coordinate low-spin d8 tbp system, the acceptor ligands prefer to occupy an equatorial site (IrCl(CO)2(PPh3)2) whereas a 7r-donor prefers an axial site. In a square pyramidal situation, it is weakly bonded acceptors that prefer the apical position, e.g. (IrCl(S02)(C0)(PPh3)2. 

Many of the nitrosyls studied are 5-coordinate, and analysis of crystallographic results indicates that, in general, in the trigonal bipyramid structures NO is found in the equatorial position in a linear geometry whereas in a square pyramidal structure, there is a bent M—N—O linkage in an apical position. A further point of interest is that in compounds like Ir(NO)Cl2(PPh3)2, the nitrosyl group bends in the more hindered (P—Ir—P) plane. 

Pi the Berry step is seen as a double bending of an equatorial and an apical angle. The two apical ligands become equatorial and two equatorial ones go to apical positions. One of the equatorial ligands, the so-called pivot, is on the fourfold axis of the tetragonal pyramidal intermediate state. The connectivity i.e. the number of isomers reached from a given one in one step, is three. 

As just mentioned, phosphorus porphyrins have unique photochemical properties. Their photophysics is also interesting. Emitter-quencher assemblies based on porphyrin building blocks have attracted attention due to their potential to serve as models in photosynthetic research (see [90] for an example) or for the development of photoswitches that could be used for the fabrication of molecular electronic/optical devices. In this context, Maiya and coworkers constructed a P(VI) porphyrin system 59b with two switchable azobenzene groups positioned in the apical positions of the pseudo-octahedral phosphorus atom [92]. Photoswitch ability (luminescence on/off) was demonstrated as... 

Rao reported measurement of third-order optical non-linearity in the nanosecond and picosecond domains for phosphorus tetratolyl porphyrins bearing two hydroxyl groups in apical position [89]. Strong nonlinear absorption was found at both 532 nm and 600 nm. The high value of nonlinearity for nanosecond pulses is attributed to higher exited singlet and triplet states. Time resolved studies indicate an ultra-fast temporal evolution of the nonlinearity in this compound. 

These complexes may be either six-coordinate with an octahedral configuration or five-coordinate with a square-pyramidal configuration, in which the organo ligand occupies the apical position a few form dimers through the interaction of each cobalt with a coordinated atom of the equatorial ligand of the other half (see Section In virtually all groups... 

Solid-state cluster chemistry is dominated by octahedral (M 5L8)L6 and (MsLi2)L units which are the focus of this paper. These two cluster types are different in the way the metal octahedral core is surrounded by the ligands. In (MsLg)L6-type clusters (Fig. 6.1a), typical for molybdenum and rhenium halides, chalcogenides, and chalcohalides, eight innei hgands (L ) cap the octahedron faces and six outer ligands (L ) are located in the apical positions [9]. For metals with a smaller number of valence electrons, the (M6L i2)L -type clusters... 

Fig. 6.1b) in which twelve inner ligands bridge the edges of the Me octahedron, and six outer ligands occupy apical positions, predominate. These units are found in reduced zirconium, niobium, tantalum, and rare-earth halides, and niobium, tantalum, molybdenum and tungsten oxides [la, 6, 10]. 

In a similar rearrangement dibenzophosphorin oxides (31) have been prepared from the reaction of dibenzophosph(ni)oles with methyl pro-piolate. Some ring expansion occurs even when R = benzyl, presumably because of the difficulty of putting benzyl in an apical position in the intermediate phosphorane. 

Treatment of the A -phospholenium salt (99) with aqueous alkali gave predominantly benzene and the oxide (100). It is suggested that here ring constraint leads to poor overlap of the 7r-bond in the ring with the p-orbital of the incipient carbanion which would lead to ring opening. Pseudorotation of the initial adduct followed by loss of the phenyl from the apical position becomes competitive. ... 

Oae found that for both base- and acid-catalyzed hydrolysis of phenyl benzenesul-fonate, there was no incorporation of 0 from solvent into the sulfonate ester after partial hydrolysis. This was interpreted as ruling out a stepwise mechanism, but in fact it could be stepwise with slow pseudorotation. In fact this nonexchange can be explained by Westheimer s rules for pseudorotation, assuming the same rules apply to pentacoordinate sulfur. For the acid-catalyzed reaction, the likely intermediate would be 8 for which pseudorotation would be disfavored because it would put a carbon at an apical position. Further protonation to the cationic intermediate is unlikely even in lOM HCl (the medium for Oae s experiments) because of the high acidity of this species a Branch and Calvin calculation (See Appendix), supplemented by allowance for the effect of the phenyl groups (taken as the difference in between sulfuric acid and benzenesulfonic acid ), leads to a pA, of -7 for the first pisTa of this cation about -2 for the second p/sTa. and about 3 for the third Thus, protonation by aqueous HCl to give the neutral intermediate is likely but further protonation to give cation 9 would be very unlikely. 

For the intermediates in base-catalyzed hydrolysis of a sulfate ester (10), pseudorotation about any of the equatorial bonds will necessarily put at least one in an apical position, which is strongly disfavored. ... 

The solid state structure of complex 7b is shown in Figure 25.1. Similar to parent chelating ether complex [9b], the solid-state structure of 7b shows a distorted square-pyramidal structure with the benzylidene moiety at the apical position. The N-aryl ring is located above the benzylidene moiety resulting in the relatively close contact of the benzylidene proton with the 7r-aromatic system of the mesityl group. 

The enantioselectivity of the BINOL-Ti(IV)-catalyzed reactions can be interpreted in terms of several fundamental structural principles.42 The aldehyde is coordinated to Ti through an apical position and there is also a 0-HC=0 hydrogen bond involving the formyl group. The most sterically favored approach of the alkene toward the complexed aldehyde then leads to the observed product. Figure 10.2 shows a representation of the complexed aldehyde and the TS structure for the reaction. 

The coordinatively flexible P/N-donor ligand PNra (411) reacts with [IrCl(cod)]2 in the presence of AgPFg to yield [Ir(cod)(PNra)](PF6), (412).665 The X-ray structure of (412) PN =i, R = H, complex confirms the cis geometry of the ligand attached via N and P donor atoms to a square-pyramidal Ir1 cod fragment with a long ethereal oxygen—Ir bond in an apical position. The Ir1... 

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... 

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