W-bonding

The W—W bond energy should be about one-sixth of the sublimation energy (note Section III-IB), and there are various schemes for estimating electronegativities, of which Mulliken s [151,152] is perhaps the most fundamental. 

The examples show Y and W coming from the same molecule, but very often (except in simultaneous addition) they come from different molecules. Also, the examples show the Y—W bond cleaving at the same time that Y is bonding to B, but often (again except for simultaneous addition) this cleavage takes place earlier. 

In—W bond. Use of Ph3Al leads to a complex in which the oxygen atom of a carbonyl ligand is the site of electron pair basicity in a WC=OAl link. Solutions of [n-Bu4N][Ph3GaCpW(CO)3] in CH2CI2 contain, in addition to free [CpW(CO)3], two isomeric complexes a metal-metal-bonded species and a C- and O-bonded adduct of the type found in the Ph3Al case. 

It is, of course, possible that there may be an intermediate in which the nitrile is w-bonded to the metal. 

As discussed in Section II. A, theoretical studies predicted that phospha-silenes with silyl substituents attached to phosphorus should have planar, trigonally coordinated silicon, with the Si—P w-bonds strengthened by the hyperconjugative influence of the silyl group.16 Recently, this was proved by a single-crystal X-ray structure determination of the derivative... 

Quite unusual reactions take place between disilenes and the active forms of the group 15 elements, P4 and As4. In nearly all reactions of disilenes, the Si—Si w-bond is broken in the first step, leaving the products isolated from the reaction of disilenes 1,11, and 12 with P4 were found to have the [1.1. OJbicyclobutane structure 698-c.98,99 In these butterflyshaped compounds the silicon atoms are completely separated, although a P—P [Pg.266]

A T structure with the strongest ct-donor D trans to the empty site (I in Scheme 1) is preferred in the case of three pure cr-donor ligands. The presence of a ir-acceptor ligand also makes the T structure more stable. When one of the ligands is a tt-donor, X, a Y structure of type II (Scheme 1) is observed. This structure permits the formation of a w bond between the empty metal d orbital and the lone pair of X. No such tt bond is present in the T structure since all symmetry adapted d orbitals are filled. This partial M—X multiple bond stabilizes Y over T. 

The shift in the C=C frequency, vi, for adsorbed ethylene relative to that in the gas phase is 23 cm-1. This is much greater than the 2 cm-1 shift that is observed on liquefaction (42) but is less than that found for complexes of silver salts (44) (about 40 cm-1) or platinum complexes (48) (105 cm-1). Often there is a correlation of the enthalpy of formation of complexes of ethylene to this frequency shift (44, 45). If we use the curve showing this correlation for heat of adsorption of ethylene on various molecular sieves (45), we find that a shift of 23 cm-1 should correspond to a heat of adsorption of 13.8 kcal. This value is in excellent agreement with the value of 14 kcal obtained for isosteric heats at low coverage. Thus, this comparison reinforces the conclusion that ethylene adsorbed on zinc oxide is best characterized as an olefin w-bonded to the surface, i.e., a surface w-complex. 

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