Square-planar

For the d-orbitals we simply obtain the transformed functions using the behaviour of the X, y, z basis so that  

From this example and Table 5.8 there are three possible outcomes for the d , dyj and d -orbital functions  

A function is unaffected by the operation. This can be the case even though the x, y and z vectors have altered for example, following the C2 operation x and y become -x and —y, but for their product the two minus signs give a plus and so xy is unaffected. In these cases a character of 1 for the function is assigned. 

A function is transformed to its own negative. This means that the areas of positive and negative phase will have been switched for the function. This could also have been achieved by a multiplication by -1. Hence, the character in this situation is -1, e.g. yz under the cr iXZ) operation. 

A function is transformed into one of the other d-functions. The d-functions are effectively our basis set in this analysis so, if a function is transformed completely into another basis function, then a character of 0 is taken, e.g. xz under the a iLZ) operation becomes yz and so would have character 0. 

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If nickel(II) cyanide, Ni(CN)2, is dissolved in excess potassium cyanide, the orange-red complex salt K2Ni(CN)4. HjO can be crystallised out this contains the stable square-planar [Ni(CN)4] anion. 

Addition of halide ions to aqueous copper(II) solutions can give a variety of halo-complexes for example [CuCl4] (yellow square-planar, but in crystals with large cations becomes a flattened tetrahedron) [CuClj] (red, units linked together in crystals to give tetrahedral or distorted octahedral coordination around each copper). 

The coefficients C are chosen to ensure that the function has a minimum at the appropriate reference bond angle. For linear, trigonal, square planar and octahedral coordination, Fourier series with just two terms are used with a Cq term and a term for n = 1, 2, 3 or 4, respectively ... 

V S, C M Kelly and C R Landis 1991. SHAPES Empirical Force-Field - New Treatment of igular Potentials and Its Application to Square-Planar Transition-Metal Complexes. Journal of American Chemical Society 113 1-12. 

Evans and co-workers investigated the effect of a number of -symmetric bis(oxazoline) ligands on the copper(II)-catalysed Diels-Alder reaction of an N-acyloxazolidinone with cyclopentadiene. Enantiomeric excesses of up to 99% have been reported (Scheme 3.4). Evans et al." suggested transition state assembly 3.7, with a square planar coordination environment around the central copper ion. In this scheme the dienophile should be coordinated predominantly in an cisoid fashion in... 

The effects of these ligands on the second-order rate constants for the Cu (ligand) catalysed reaction of Ic with 2 are modest In contrast, the effects on IC2 are more pronounced. The aliphatic Oramino acids induce an approximately two-fold reduction of Iv relative to for the Cu" aquo ion. For the square planar coordinated copper ions this effect is expected on the basis of statistics. The bidentate ligands block half the sites on the copper centre. 

Atoms with unusual hybridizations can be particularly dihicult to include. Most organic force helds describe atoms with hybridizations whose bond angles are all equivalent (i.e., sp, sp, and sp hybridizations with bond angles of 180, 120, and 109.5°, respectively). In contrast to this, a square planar atom will have some bond angles of 90° and some angles of 180°. In this case, it may be necessary to dehne the bond and angle terms manually, modify the software, or hold the bond angles hxed in the calculation. 

Gold Compounds. The chemistry of nonmetallic gold is predominandy that of Au(I) and Au(III) compounds and complexes. In the former, coordination number two and linear stereochemistry are most common. The majority of known Au(III) compounds are four coordinate and have square planar configurations. In both of these common oxidation states, gold preferably bonds to large polarizable ligands and, therefore, is termed a class b metal or soft acid. 

Simple nickel salts form ammine and other coordination complexes (see Coordination compounds). The octahedral configuration, in which nickel has a coordination number (CN) of 6, is the most common stmctural form. The square-planar and tetrahedral configurations (11), iu which nickel has a coordination number of 4, are less common. Generally, the latter group tends to be reddish brown. The 5-coordinate square pyramid configuration is also quite common. These materials tend to be darker in color and mostiy green (12). 

The most common oxidatiou states and corresponding electronic configurations of rhodium are +1 which is usually square planar although some five coordinate complexes are known, and +3 (t7 ) which is usually octahedral. Dimeric rhodium carboxylates are +2 (t/) complexes. Compounds iu oxidatiou states —1 to +6 (t5 ) exist. Significant iudustrial appHcatious iuclude rhodium-catalyzed carbouylatiou of methanol to acetic acid and acetic anhydride, and hydroformylation of propene to -butyraldehyde. Enantioselective catalytic reduction has also been demonstrated. 

The most common oxidation states and corresponding electronic configurations of platiaum are +2 which is square planar, and +4 which is octahedral. Compounds in oxidation states between 0 and +6 [t) exist. Platiaum hydrosilation catalysts are used in the manufacture of siHcone polymers. Several platiaum coordination compounds are important chemotherapeutic agents used for the treatment of cancer. 

For tetranuclear cluster complexes, three stmcture types are observed tetrahedral open tetrahedral (butterfly) or square planar, for typical total valence electron counts of 60, 62, and 64, respectively. The earliest tetracarbonyl cluster complexes known were Co4(CO)22, and the rhodium and iridium analogues. The... 

Discernible associative character is operative for divalent 3t5 ions through manganese and the trivalent ions through iron, as is evident from the volumes of activation in Table 4. However, deprotonation of a water molecule enhances the reaction rates by utilising a conjugate base 7T- donation dissociative pathway. As can be seen from Table 4, there is a change in sign of the volume of activation AH. Four-coordinate square-planar molecules also show associative behavior in their reactions. 

For many species the effective atomic number (FAN) or 18- electron rule is helpful. Low spin transition-metal complexes having the FAN of the next noble gas (Table 5), which have 18 valence electrons, are usually inert, and normally react by dissociation. Fach normal donor is considered to contribute two electrons the remainder are metal valence electrons. Sixteen-electron complexes are often inert, if these are low spin and square-planar, but can undergo associative substitution and oxidative-addition reactions. 

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