Back-bonds

Th e ability to perform m oleciilar orbital (MO ) calculation s on m et-als is extremely useliil because molecular mechanics methods are gen erally unable to treat m etals. This is becau se m etals h ave a wide range of valences, oxidation states, spin multiplicities, and have 1111 usual bonding situations (e.g.. d%-p% back bonding). In addition. the 11 on direction al n at are o ( m etallic hon din g is less am en a-ble to a ball and spring interpretation. 

Electron correlation is often very important as well. The presence of multiple bonding interactions, such as pi back bonding, makes coordination compounds more sensitive to correlation than organic compounds. In some cases, the HF wave function does not provide even a qualitatively correct description of the compound. If the weight of the reference determinant in a single-reference CISD calculation is less than about 0.9, then the HF wave function is not qualitatively correct. In such cases, multiple-determinant, MSCSF, CASPT2, or MRCI calculations tend to be the most efficient methods. The alternative is... 

Perhaps because of inadequate or non-existent back-bonding (p. 923), the only neutral, binary carbonyl so far reported is Ti(CO)g which has been produced by condensation of titanium metal vapour with CO in a matrix of inert gases at 10-15 K, and identified spectroscopically. By contrast, if MCI4 (M = Ti, Zr) in dimethoxy-ethane is reduced with potassium naphthalenide in the presence of a crown ether (to complex the K+) under an atmosphere of CO, [M(CO)g] salts are produced. These not only involve the metals in the exceptionally low formal oxidation state of —2 but are thermally stable up to 200 and 130°C respectively. However, the majority of their carbonyl compounds are stabilized by n-bonded ligands, usually cyclopentadienyl, as in [M(/j5-C5H5)2(CO)2] (Fig. 21.8). 

Structures have been determined for a number of these compounds, showing that the Rh-P bonds are little affected by the m-ligands (Figure 2.22). The shorter Rh-C distance in the thiocarbonyl is probably a result of greater Rh=C back-bonding. Addition of S02 results in the formation of a 5-coordinate (sp) adduct with the expected lengthening in all bonds. 

Calculations for trigonal bipyramidal ML4(NO) systems with axial NO-like [Ir(NO)(PPh3)3H+] give a d orbital sequence of xz,yz < x2 — y2, xy < z2 so that in such an IrNO 8 system, the z2 orbital is unoccupied not only does bending not produce any stabilization but in fact dxz, dyz — 7r back-bonding is lost, favouring a linear Ir—N—O bond. 

There is (a) cr-donation from a filled oxygen orbital to an empty platinum orbital and (b) 7r back-bonding from a filled metal d orbital into an empty oxygen 7r -anti-bonding orbital. 

Back-bonding, with formation of a 7r-bond, from a filled metal d orbital to an anti-bonding it -ethene orbital. 

Multiple Bonds and Back-bonding (see also Tables 3.23. 6.10 and 21.2)... 

Figure 6-13. Synergic back-bonding in a platinum alkene complex. In (a), the interaction of a (filled) platinum 5d orbital with the tf molecular orbital of the alkene is shown, whilst in (b), the interaction of a dsp hybrid orbital with the n molecular orbital of the alkene is shown. Note that the two interactions result in electron density moving in opposite directions.

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