Metal ligand multiple bond
Encyclopedia
In Chemistry, a metal–ligand multiple bond describes the interaction of certain ligand
Ligand
In coordination chemistry, a ligand is an ion or molecule that binds to a central metal atom to form a coordination complex. The bonding between metal and ligand generally involves formal donation of one or more of the ligand's electron pairs. The nature of metal-ligand bonding can range from...

s with a metal with a bond order
Bond order
Bond order is the number of chemical bonds between a pair of atoms. For example, in diatomic nitrogen N≡N the bond order is 3, while in acetylene H−C≡C−H the bond order between the two carbon atoms is also 3, and the C−H bond order is 1. Bond order gives an indication to the stability of a bond....

 greater than one. Coordination complexes featuring multiply bonded ligands are of both scholarly and practical interest. Transition metal carbene complex
Transition metal carbene complex
A transition metal carbene complex is a organometallic compound featuring a divalent organic ligand. The divalent organic ligand coordinated to the metal center is called a carbene. Carbene complexes for almost all transition metals have been reported. Many methods for synthesizing them and...

es catalyze the olefin metathesis
Olefin metathesis
Olefin metathesis or transalkylidenation is an organic reaction that entails redistribution of alkylene fragments by the scission of carbon - carbon double bonds in olefins . Its advantages include the creation of fewer sideproducts and hazardous wastes. Yves Chauvin, Robert H. Grubbs, and Richard R...

 reaction. Metal oxo intermediates are pervasive in oxidation catalysis. oxygen evolving complex
Oxygen evolving complex
The oxygen-evolving complex, also known as the water-splitting complex, is a water-oxidizing enzyme involved in the photooxidation of water during the light reactions of photosynthesis. Based on a widely accepted theory from 1970 by Kok, the complex can exist in 5 states: S0 to S4. Photons trapped...

.


As a cautionary note, the classification of a metal ligand bond as being "multiple" bond order is ambiguous and even arbitrary because bond order
Bond order
Bond order is the number of chemical bonds between a pair of atoms. For example, in diatomic nitrogen N≡N the bond order is 3, while in acetylene H−C≡C−H the bond order between the two carbon atoms is also 3, and the C−H bond order is 1. Bond order gives an indication to the stability of a bond....

 is a formalism. Furthermore, the usage of multiple bonding is not uniform. Symmetry arguments suggest that most ligands engage metals via multiple bonds. The term 'metal ligand multiple bond" is often reserved for ligands of the type CRn and NRn (n = 0, 1, 2) and ORn (n = 0, 1) where R is H or an organic substituent, or pseudohalide. Historically, CO and NO+ are not included in this classification, nor are halides.

Pi-donor ligands

In coordination chemistry, a pi-donor ligand is a kind of ligand endowed with filled non-bonding orbitals that overlap with metal-based orbitals. Their interaction is complementary to the behavior of pi-acceptor ligands. The existence of terminal oxo ligand
Oxo ligand
In coordination chemistry, an oxo ligand is an oxygen atom bound only to one or more metal centers. These ligands can exist as terminal or as bridging atom . Oxo ligands stabilize high oxidation states of a metal....

s for the early transition metals is one consequence of this kind of bonding. Classic pi-donor ligands are oxide (O2-), nitride (N3-), imide (RN2-), alkoxide (RO-), amide (R2N-), and fluoride. For late transition metals, strong pi-donors form anti-bonding interactions with the filled d-levels, with consequences for spin state, redox potentials, and ligand exchange rates. Pi-donor ligands are low in the spectrochemical series
Spectrochemical series
A spectrochemical series is a list of ligands ordered on ligand strength and a list of metal ions based on oxidation number, group and its identity...

.

Multiple bond stabilization

Metals bound to so-called triply bond
Triple bond
A triple bond in chemistry is a chemical bond between two chemical elements involving six bonding electrons instead of the usual two in a covalent single bond. The most common triple bond, that between two carbon atoms, can be found in alkynes. Other functional groups containing a triple bond are...

ed carbyne
Carbyne
In chemistry, a carbyne is a monovalent carbon radical species containing an electrically neutral univalent carbon atom with three non-bonded electrons.- Gas phase/reactive intermediate :...

, imide
Imide
In organic chemistry, an imide is a functional group consisting of two carbonyl groups bound to nitrogen. These compounds are structurally related to acid anhydrides. The relationship between esters and amides and between imides and anhydrides is analogous, the amine-derived groups are less reactive...

 , nitride
Nitride
In chemistry, a nitride is a compound of nitrogen where nitrogen has a formal oxidation state of −3. Nitrides are a large class of compounds with a wide range of properties and applications....

 (nitrido), and oxide
Oxide
An oxide is a chemical compound that contains at least one oxygen atom in its chemical formula. Metal oxides typically contain an anion of oxygen in the oxidation state of −2....

 (oxo) ligands are generally assigned to high oxidation states with low d electron counts. The high oxidation state
Oxidation state
In chemistry, the oxidation state is an indicator of the degree of oxidation of an atom in a chemical compound. The formal oxidation state is the hypothetical charge that an atom would have if all bonds to atoms of different elements were 100% ionic. Oxidation states are typically represented by...

 stabilizes the highly reduced ligands. The low d electron count
D electron count
The d electron count is a chemistry formalism used to describe the electron configuration of the valence electrons of a transition metal center in a coordination complex. The d electron count is an effective way to understand the geometry and reactivity of transition metal complexes...

 allow for many bonds between ligands and the metal center. A d0 metal center can accommodate up to 9 bonds without violating the 18 electron rule, whereas a d6 species can only accommodate 6 bonds.

Reactivity explained through ligand hybridization

A ligand described in ionic terms can bond to a metal through however many lone pairs it has available. For example many alkoxides use one of their three lone pairs to make a single bond to a metal center. In this situation the oxygen is sp3 hybridized
Orbital hybridisation
In chemistry, hybridisation is the concept of mixing atomic orbitals to form new hybrid orbitals suitable for the qualitative description of atomic bonding properties. Hybridised orbitals are very useful in the explanation of the shape of molecular orbitals for molecules. It is an integral part...

 according to valence bond theory
Valence bond theory
In chemistry, valence bond theory is one of two basic theories, along with molecular orbital theory, that were developed to use the methods of quantum mechanics to explain chemical bonding. It focuses on how the atomic orbitals of the dissociated atoms combine to give individual chemical bonds...

. Increasing the bond order to two by involving another lone pair changes the hybridization at the oxygen to an sp2 center with an expected expansion in the M-O-R bond angle and contraction in the M-O bond length. If all three lone pairs are included for a bond order of three than the M-O bond distance contracts further and since the oxygen is a sp center the M-O-R bond angle is 180˚ or linear. Similarly with the imidos are commonly referred to as either bent (sp2) or linear (sp). Even the oxo can be sp2 or sp hybridized. The triply bonded oxo, similar to carbon monoxide
Carbon monoxide
Carbon monoxide , also called carbonous oxide, is a colorless, odorless, and tasteless gas that is slightly lighter than air. It is highly toxic to humans and animals in higher quantities, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal...

, is partially positive at the oxygen atom and unreactive towards bronsted acids at the oxygen atom. When such a complex is reduced, the triple bond can be converted to a double bond
Double bond
A double bond in chemistry is a chemical bond between two chemical elements involving four bonding electrons instead of the usual two. The most common double bond, that between two carbon atoms, can be found in alkenes. Many types of double bonds between two different elements exist, for example in...

 at which point the oxygen no longer bears a partial positive charge and is reactive towards acid.

Bonding representations

Imido ligands, also known as imides or nitrenes, most commonly form "linear six electron bonds" with metal centers. Bent imidos are a rarity limited by complexes electron count, orbital bonding availability, or some similar phenomenon. It is common to draw only two lines of bonding for all imidos, including the most common linear imidos with a six electron bonding interaction to the metal center. Similarly amido complexes are usually drawn with a single line even though most amido bonds involve four electrons. Alkoxides are generally drawn with a single bond although both two and four electron bonds are common. Oxo can be drawn with two lines regardless of whether four electrons or six are involved in the bond, although it is not uncommon to see six electron oxo bonds represented with three lines.

Representing oxidation states

There are two motifs to indicate a metal oxidation state based around the actual charge separation of the metal center. Oxidation states up to +3 are believed to be an accurate representation of the charge separation experienced by the metal center. For oxidation states of +4 and larger, the oxidation state becomes more of a formalism with much of the positive charge distributed between the ligands. This distinction can be expressed by using a Roman numeral for the lower oxidation states in the upper right of the metal atomic symbol and an Arabic number with a plus sign for the higher oxidation states (see the example below). This formalism is not rigorously followed and the use of Roman numerals to represent higher oxidation states is common.
[MIIILn]3+ vs. [O=M5+Ln]3+

Further reading (specialized literature)

  • Heidt, L.J.; Koster, G.F.; Johnson, A.H. "Experimental and Crystal Field Study of the Absorption Spectrum at 2000 to 8000 A of to Manganous Perchlorate in Aqueous Perchloric Acid" J. Am. Chem. Soc. 1959, 80, 6471–6477.
  • Rohde,J; In,J.; Lim, M.H.; Brennessel, W.W.; Bukowski, M.R.; Stubna, A.; Muonck, E.; Nam, W.; Que L. "Crystallographic and Spectroscopic Characterization of a Nonheme Fe(IV)O Complex" Science
    Science (journal)
    Science is the academic journal of the American Association for the Advancement of Science and is one of the world's top scientific journals....

    VOL 299 1037–1039.
  • Decker, A.; Rohde,J.; Que, L.; Solomon, E.I.
    Edward I. Solomon
    Professor Edward I. Solomon is the current Monroe E. Spaght Professor of Chemistry at Stanford University. He is an elected member of the United States National Academy of Sciences, a Fellow of the American Association for the Advancement of Science, and a Fellow of the American Academy of Arts...

     "Spectroscopic and Quantum Chemical Characterization of the Electronic Structure and Bonding in a Non-Heme FeIVO Complex" J. Am. Chem. Soc. 2004, 126, 5378–5379.
  • Aliaga-Alcalde, N.; George, S.D.; Mienert, B.; Bill, E.; Wieghardt, K.; Neese, F. "The Geometric and Electronic Structure of [(cyclam-acetato)Fe(N)]+: A Genuine Iron(V) Species with a Ground-State Spin S=1/2" Angew. Chem. Int. Ed.
    Angewandte Chemie
    Angewandte Chemie is a weekly peer-reviewed scientific journal that covers all aspects of chemistry. Its impact factor was 12.730 in 2010, the highest value for a chemistry-specific journal that publishes original research...

    2005, 44, 2908–2912.
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