Ligand bond number

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Ligand bond number (LBN) represents the effective total number of ligands or ligand attachment points surrounding a metal center, labeled M. [1] [2] More simply, it represents the number of coordination sites occupied on the metal. Based on the covalent bond classification method (from where LBN is derived), the equation for determining ligand bond number is as follows:

Contents

LBN = L + X + Z

Where L represents the number of neutral ligands adding two electrons to the metal center (typically lone electron pairs, pi-bonds and sigma bonds. Most encountered ligands will fall under this category. X represents covalent-bonding ligands such as halogen anions. Z represents, though rarely encountered electron accepting ligands or dative bond forming ligands. The ligand bond number convention is most commonly encountered within inorganic chemistry and it's related fields organometallic chemistry and bioinorganic chemistry.

Comparisons with Coordination Number

On comparison to the classical coordination numbers, some major differences can be seen. For example, (η5cyclopentadienyl)2Cr (ML4X2) and (η6benzene)2Cr (ML6) both have a LBN of 6 as compared to classical coordination numbers of 10 and 12. [3] Well known complexes such as Ferrocene and Uranocene also serve as examples where LBN and coordination number differ. Ferrocene has two η5 cyclopentadienyl ligands while Uranocene has two η8 cyclooctatetraene ligands; however, by covalent bond classification the complexes are found to be ML4X2 and ML6X4. [4] This corresponds to LBN values of 6 and 10 respectively, even though the total coordination numbers would be 10 and 16. The usefulness of LBN to describe bonding extends beyond just sandwich compounds. Co(CO)3(NO) is a stable 18-electron complex in part due to the bonding of the NO ligand in its linear form. The donation of the lone pair on the nitrogen makes this complex ML4X, containing 18 electrons. The traditional coordination number here would be 4, while the CBC more accurately describes the bonding with a LBN of 5. In simple cases, the LBN is often equal to the classical coordination number (ex. Fe(CO)5, etc.) [5]

Eta5CP2Cr.png
Eta62Cr.png
Example of Chromium coordination complexes with differing LBN and Cord#.

Left5–cyclopentadienyl)2Cr: LBN of 6, Coordination # of 10

Right6–benzene)2Cr: LBN of 6, Coordination # of 12

Ligand bond plots

The LBN for transition metals trends downward from left to right across the periodic table. This trend is highlighted in the LBN plots of Groups 3 through 10. Groups exhibit trends, but the LBN for individual complexes can vary.

Related Research Articles

Electron counting is a formalism used for classifying compounds and for explaining or predicting electronic structure and bonding. Many rules in chemistry rely on electron-counting:

Ligand Chelating or binding agent

In coordination chemistry, a ligand is an ion or molecule that binds to a central atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs often through Lewis Bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands".

Metallocene

A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5
H
5
, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride, vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.

Ferrocene is an organometallic compound with the formula Fe(C
5
H
5
)
2
. The molecule consists of two cyclopentadienyl rings bound on opposite sides of a central iron atom. It is an orange solid with a camphor-like odor, that sublimes above room temperature, and is soluble in most organic solvents. It is remarkable for its stability: it is unaffected by air, water, strong bases, and can be heated to 400 °C without decomposition. In oxidizing conditions it can reversibly react with strong acids to form the ferrocenium cation Fe(C
5
H
5
)+
2
.

Cyclopentadienyl complex

A cyclopentadienyl complex is a metal complex with one or more cyclopentadienyl groups. Cyclopentadienyl ligands almost invariably bind to metals as a pentahapto (η5-) bonding mode. The metal–cyclopentadienyl interaction is typically drawn as a single line from the metal center to the center of the Cp ring.

Isolobal principle

The isolobal principle is a strategy used in organometallic chemistry to relate the structure of organic and inorganic molecular fragments in order to predict bonding properties of organometallic compounds. Roald Hoffmann described molecular fragments as isolobal "if the number, symmetry properties, approximate energy and shape of the frontier orbitals and the number of electrons in them are similar – not identical, but similar." One can predict the bonding and reactivity of a lesser-known species from that of a better-known species if the two molecular fragments have similar frontier orbitals, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Isolobal compounds are analogues to isoelectronic compounds that share the same number of valence electrons and structure. A graphic representation of isolobal structures, with the isolobal pairs connected through a double-headed arrow with half an orbital below, is found in Figure 1.

Cobaltocene Chemical compound

Cobaltocene, known also as bis(cyclopentadienyl)cobalt(II) or even "bis Cp cobalt", is an organocobalt compound with the formula Co(C5H5)2. It is a dark purple solid that sublimes readily slightly above room temperature. Cobaltocene was discovered shortly after ferrocene, the first metallocene. Due to the ease with which it reacts with oxygen, the compound must be handled and stored using air-free techniques.

Hapticity

Hapticity is the coordination of a ligand to a metal center via an uninterrupted and contiguous series of atoms. The hapticity of a ligand is described with the Greek letter η ('eta'). For example, η2 describes a ligand that coordinates through 2 contiguous atoms. In general the η-notation only applies when multiple atoms are coordinated. In addition, if the ligand coordinates through multiple atoms that are not contiguous then this is considered denticity, and the κ-notation is used once again. When naming complexes care should be taken not to confuse η with μ ('mu'), which relates to bridging ligands.

Chromocene Chemical compound

Chromocene is the organochromium compound with the formula [Cr(C5H5)2]. Like structurally related metallocenes, chromocene readily sublimes in a vacuum and is soluble in non-polar organic solvents. It is more formally known as bis(η5-cyclopentadienyl)chromium(II).

Sandwich compound

In organometallic chemistry, a sandwich compound is a chemical compound featuring a metal bound by haptic covalent bonds to two arene ligands. The arenes have the formula CnHn, substituted derivatives (for example Cn(CH3)n) and heterocyclic derivatives (for example BCnHn+1). Because the metal is usually situated between the two rings, it is said to be "sandwiched". A special class of sandwich complexes are the metallocenes.

Organoactinide chemistry

Organoactinide chemistry is the science exploring the properties, structure and reactivity of organoactinide compounds, which are organometallic compounds containing a carbon to actinide chemical bond.

Organotitanium compound

Organotitanium compounds in organometallic chemistry contain carbon-to-titanium chemical bonds. Organotitanium chemistry is the science of organotitanium compounds describing their physical properties, synthesis and reactions. They are reagents in organic chemistry and are involved in major industrial processes.

Organouranium chemistry

Organouranium chemistry is the science exploring the properties, structure and reactivity of organouranium compounds, which are organometallic compounds containing a carbon to uranium chemical bond. The field is of some importance to the nuclear industry and of theoretical interest in organometallic chemistry.

In organometallic chemistry, a transition metal indenyl complex is a coordination compound that contains one or more indenyl ligands. The indenyl ligand is formally the anion derived from deprotonation of indene. The η5-indenyl ligand is related to the η5cyclopentadienyl anion (Cp), thus indenyl analogues of many cyclopentadienyl complexes are known. Indenyl ligands lack the 5-fold symmetry of Cp, so they exhibit more complicated geometries. Furthermore, some indenyl complexes also exist with only η3-bonding mode. The η5- and η3-bonding modes sometimes interconvert.

In chemistry, π-effects or π-interactions are a type of non-covalent interaction that involves π systems. Just like in an electrostatic interaction where a region of negative charge interacts with a positive charge, the electron-rich π system can interact with a metal, an anion, another molecule and even another π system. Non-covalent interactions involving π systems are pivotal to biological events such as protein-ligand recognition.

Organoscandium chemistry is the chemistry of organometallic compounds containing a carbon to scandium chemical bond. The interest in organoscandium compounds is mostly academic but several compound classes find practical application in catalysis, especially in polymerization. A common precursor is scandium chloride.

Rhodocene chemical compound

Rhodocene is a chemical compound with the formula [Rh(C5H5)2]. Each molecule contains an atom of rhodium bound between two planar aromatic systems of five carbon atoms known as cyclopentadienyl rings in a sandwich arrangement. It is an organometallic compound as it has (haptic) covalent rhodium–carbon bonds. The [Rh(C5H5)2] radical is found above 150 °C or when trapped by cooling to liquid nitrogen temperatures (−196 °C). At room temperature, pairs of these radicals join via their cyclopentadienyl rings to form a dimer, a yellow solid.

The covalent bond classification (CBC) method is also referred to as the LXZ notation. It was published by M. L. H. Green in 1995 as a solution for the need to describe covalent compounds such as organometallic complexes in a way that is not prone to limitations resulting from the definition of oxidation state. Instead of simply assigning a charge to an atom in the molecule, the covalent bond classification method analyzes the nature of the ligands surrounding the atom of interest, which is often a transition metal. According to this method, there are three basic types of interactions that allow for coordination of the ligand. The three types of interaction are classified according to whether the ligating group donates two, one, or zero electrons. These three classes of ligands are respectively given the symbols L, X, and Z.

Transition-metal allyl complex

Transition-metal allyl complexes are coordination complexes with allyl and its derivatives as ligands. Allyl is the radical with the connectivity CH2CHCH2, although as a ligand it is usually viewed as an allyl anion CH2=CH−CH2, which is usually described as two equivalent resonance structures.

Magnesocene, also known as bis(cyclopentadienyl)magnesium(II) and sometimes abbreviated as MgCp2, is an organometallic compound with the formula Mg(η5-C5H5)2. It is an example of an s-block main group sandwich compound, structurally related to the d-block element metallocenes, and consists of a central magnesium atom sandwiched between two cyclopentadienyl rings.

References

  1. Green, M.L.H. (1995). "A new approach to the formal classification of covalent compounds of the elements". J. Organomet. Chem. 500 (1): 127–148. doi:10.1016/0022-328X(95)00508-N.
  2. Crabtree, Robert (2005). The Organometallic Chemistry of the Transition Metals: 4th Edition. Wiley-Interscience.
  3. Crabtree, Mingos (2007). Comprehensive Organometallic Chemistry Vol. 1. Oxford: Elsevier. pp. 31–33.
  4. Streitwieser, A.; Mueller-Westerhoff, U. (1968). "Bis(cyclooctatetraenyl)uranium (uranocene). A new class of sandwich complexes that utilize atomic f orbitals". J. Am. Chem. Soc. 90 (26): 7364. doi:10.1021/ja01028a044.
  5. Spessard, Gary; Miessler, G. (2010). Organometallic Chemistry: 2nd Edition. Oxford University Press.