Covalent bond transition metal compounds

The general understanding of the electronic structure and the bonding properties of transition-metal silicides is in terms of low-lying Si(3.s) and metal-d silicon-p hybridization. There are two dominant contributions to the bonding in transition-metal compounds, the decrease of the d band width and the covalent hybridization of atomic states. The former is caused by the increase in the distance between the transition-metal atoms due to the insertion of the silicon atoms, which decreases the d band broadening contribution to the stability of the lattice. 

The covalency contraction parameter, Rv, which measures the volume of a transition metal compound MmX relative to the volume of MgmXn, is proportional to the electronegativity of X and thus decreases as the covalence of the M—X bond increases. 

In general, overlap of incompletely filled p orbitals results in large deviations from pure ionic bonding, and covalent interactions result. Incompletely filled / orbitals are usually well shielded from the crystal field and behave as essentially spherical orbitals. Incompletely filled d orbitals, on the other hand, have a large effect on the energetics of transition metal compounds and here the so-called crystal field effects become important. 

Both cationic adsorption and anionic adsorption belong to what is called ionic adsorption. Covalent adsorption is due to the localized covalent bonding, and metallic adsorption is due to the delocalized covalent bonding. The distinction among these three modes of chemisorption, however, is not so definite that the transition from the covalent through the metallic to the ionic adsorption may not be discontinuous, but rather continuous, in the same way as the transition of the three-dimensional solid compounds between the covalent, metallic, and ionic bonding. 

Especially, the subdivision in different hydrogen bond acceptor atom sets improves the performance of the SEN approach while a subdivision depending on the hydrogen bond donor atom showed only a minor improvement compared to the general fit of Reiher et al. Thus, the SEN approach has proven as a tool to investigate hydrogen bonds of, e.g., transition metal compounds (171,174-177), peptides (178), enzymes (179), DNA and RNA (173), molecular switches (180), ionic liquids (181,182), and rotaxanes (183). However, the SEN approach is not solely restricted to hydrogen bond detection. This approach can also be apphed to determine the covalent interaction between metal atoms (184) or phosphorus atoms (162,185). Therefore, it is suitable for different kind of interactions. 

Transition metal compounds with covalent carbon-metal bonds include organo-zinc, organo-cadmium, and organo-mercury compounds. Carbon-13 shifts of the methyl derivatives (Table 4.71) indicate a heavy atom deshielding. Diphenylmercury displays carbon shifts similar to those of phenyllithium and phenylmagnesium bromide (Table 4.53). 

In this chapter, we ll look at the properties and chemical behavior of transition metal compounds, paying special attention to coordination compounds, in which a central metal ion (or atom)—usually a transition metal—is attached to a group of surrounding molecules or ions by coordinate covalent bonds (Section 7.5). 

Dative covalent bonds, or coordinate covalent bonds, are those in which electrons are shared (as in all covalent bonds), but in which both electrons involved in each bond are contributed from the same atom. Such bonds occur in organometallic compounds of transition metals having vacant d orbitals. It is beyond the scope of this book to discuss such bonding in detail the reader needing additional information should refer to works on organometallic compounds.12 The most common organometallic compounds that have dative covalent bonds are carbonyl compounds, which are formed from a transition metal and carbon monoxide, where the metal is usually in the -1, 0, or +1 oxidation state. In these compounds the carbon atom on the carbon monoxide acts as an electron-pair donor ... 

The results for Cr34 and the 3d5 cations Fe3+ and Mn2+ show that it is possible to derive values of the Racah B parameter for transition metal compounds from absorption bands in their crystal field spectra, enabling comparisons to be made with field-free ion values. In all cases, there is a decrease of the Racah B parameter for the bonded cations relative to the gaseous ions, which is indicative of diminished repulsion between 3d electrons in chemical compounds of the transition metals. This reduction is attributable to electron delocalization or covalent bonding in the compounds. Such decreases of Racah B parameters are expressed as the nephelauxetic Greek , cloud expanding) ratio, p, given by... 

Supports used for obtaining Ziegler-Natta catalysts can differ essentially from one another. Some of the supports may contain reactive surface groups (such as hydroxyl groups present in specially prepared metal oxides) while others do not contain such reactive functional groups (such as pure anhydrous metal chlorides). Therefore, the term supported catalyst is used in a very wide sense. Supported catalysts comprise not only systems in which the transition metal compound is linked to the support by means of a chemical covalent bond but also systems in which the transition metal atom may occupy a position in a lattice structure, or where complexation, absorption or even occlusion may take place [28]. The transition metal may also be anchored to the support via a Lewis base in such a case the metal complexes the base, which is coordinatively fixed on the support surface [53,54]. 

Supported precursors for Ziegler-Natta catalysts may be obtained, depending on the kind of support, in two ways by treatment of the support containing surface hydroxyl groups with a transition metal compound with chemical covalent bond formation, and by the treatment of a magnesium alkoxide or magnesium chloride support with a Lewis base and transition metal compound with coordination bond formation. 

The dimensionality of the space spanned by covalent states is much less than the full number of basis states of the Hubbard model. This is one of the reasons of the success in the application of the above VB Hamiltonians to the study of low-lying energy levels of the transition metal compounds and organic molecules with conjugated bonds. The covalent VB approach is very useful especially for predictions as to ground state spin multiplicity and spin ordering [14,17-20],... 

Boreskov (18) has proposed a model for transition metal compounds in which the rate of oxidation is assumed to be determined by the rate of electron transfer between oxygen and the transition metal ion. This process is further assumed to be facilitated with increasing degree of covalency of the metal-oxygen bond. Thus the more covalent transition metal oxides are more active than the rather ionic metal ion-exchanged zeolites. The oxygen-bridged species as described above is considered to be more covalent in character, and hence more active for oxidation catalysis than the transition... 

The rate and extent of the dissociation are dependent upon the ligands of the transition metal compound (see Fig. 11 and Table II). This can be understood only if there is a covalent bond between the N atoms and the metal.11... 

Let us look first for transition-metal compounds that arc truly covalent in the sense of tetrahedral structures and two-electron bonds, which we di.scu.sscd earlier. There are only a few examples. NbN and TaN both form in the wurtzite structure. We presume that bond orbitals of sp hybrids must be present to stabilize the structure this requires three electrons from each transition-metal ion. Both ions are found in column D5 of the Solid State Table, so we anticipate that the remaining two electrons would form a multiplet (as in the ground stale of Ti " ). Thus the effects of the d state are simply added onto an otherwise simple covalent system, just as they were added to a simple ionic system in the monoxides. MnS, MnSe, and MnTe also form a wurtzite structure and presumably may be understood in just the same way. This class of compounds is apparently too small to have been studied extensively. 

Didziulis, S. V., S. L. Cohen, K. D. Butcher, and E. I. Solomon (1988). Variable photon energy photoelectron spectroscopic studies of covalent bonding in Sd " transition-metal compounds. Inorg. Chem. 27, 2238-50. 

The directionality in the bonding between a d-block metal ion and attached groups such as ammonia or chloride can now be understood in terms of the directional quality of the d orbitals. In 1929, Bethe described the crystal field theory (CFT) model to account for the spectroscopic properties of transition metal ions in crystals. Later, in the 1950s, this theory formed the basis of a widely used bonding model for molecular transition metal compounds. The CFT ionic bonding model has since been superseded by ligand field theory (LFT) and the molecular orbital (MO) theory, which make allowance for covalency in the bonding to the metal ion. However, CFT is still widely used as it provides a simple conceptual model which explains many of the properties of transition metal ions. 

Against this view are comprehensive theoretical studies which put only a single covalent dr-Pr bond between the metal and the ring in all the transition metal compounds ( 3, 26, 32, 119, 131). On this basis, ferrocene, for example, should show only a closed 3d shell. Four -electrons would then remain in the rings, which could be considered as radicals, without taking part in the bonding. 

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