Transition metal fullerene complex

Last updated
Structure of C60[IrCl(CO)(PMe3)2]2. Color code: green = Cl, blue = Ir, ochre = P YEMVOB.png
Structure of C60[IrCl(CO)(PMe3)2]2. Color code: green = Cl, blue = Ir, ochre = P

A transition metal fullerene complex is a coordination complex wherein fullerene serves as a ligand. Fullerenes are typically spheroidal carbon compounds, the most prevalent being buckminsterfullerene, C60. [2]

Contents

One year after it was prepared in milligram quantities in 1990, [3] C60 was shown to function as a ligand in the complex [Ph3P]2Pt(η2-C60). [4]

Since this report, a variety of transition metals and binding modes were demonstrated. Most transition metal fullerene complex are derived from C60, although other fullerenes also coordinate to metals as seen with C70Rh(H)(CO)(PPh3)2. [5]

Binding modes

As ligands, fullerenes behave similarly to electron-deficient alkenes such as tetracyanoethylene. Thus, their complexes are a subset of metal-alkene complexes. They almost always coordinate in a dihapto fashion and prefer electron-rich metal centers. [6] This binding occurs on the junction of two 6-membered rings. Hexahapto and pentahapto bonding is rarely observed. [7]

In Ru3(CO)9(C60), the fullerene binds to the triangular face of the cluster. [8]

Examples

C60 forms stable complexes of the type M(C60)(diphosphine)(CO)3 for M = Mo, W. A dirhenium complexes is known with the formula Re2(PMe3)4H822C60) where two of the hydrogen act as bridging ligands. [5]

Many fullerene complexes are derived from platinum metals. An unusual cationic complex features three 16e Ru centers:

3 Cp*Ru(MeCN)3+ + C60 → {[(Cp*Ru(MeCN)2]3C60}3+ + 3 MeCN

Vaska's complex forms a 1:1 adduct, and the analogous IrCl(CO)(PEt3)2 binds 200x more strongly. [2] Complexes with more than one fullerene ligand are illustrated by Ir4(CO)34-CH)(PMe3)2(μ-PMe)2(CNCH2Ph)(μ-η22C60)(μ41122C60). In this Ir4 cluster two fullerene ligands with multiple types of mixed binding. Platinum, palladium, and nickel form complexes of the type C60ML2 where L is a monodentate or bidentate phosphorus ligand. [5] They are prepared by displacement of weakly coordinating ligands such as ethylene: [6]

[Ph3P]2Pt(C2H4) + C60 → [Ph3P]2Pt(η2-C60) + C2H4

In [(Et3P)2Pt]62-C60), six Pt centers are bound to the fullerene. [9]

Modified fullerenes as ligands

Osmium tetraoxide adds to C60 to give, in the presence of pyridine (py), the diolate C60O2OsO2(py)2. [2]

The pentaphenyl anion C60Ph5 behaves as a cyclopentadienyl ligand. [5]

Ferrocene-like complex of C60Ph5 . Fullerene 3.png
Ferrocene-like complex of C60Ph5 .

In this example, the binding of the ligand is similar to ferrocene. The anion C60(PhCH2)2Ph functions as an indenyl-like ligand. [10] Fullerenes can also be substituents on otherwise conventional ligands as seen with an isoxazoline fullerene chelating to platinum, rhenium, and iridium compounds. [11]

Ongoing research

Although no application has been commercialized. non-linear optical (NLO) materials, [12] and as supramolecular building blocks. [13]

See also

Related Research Articles

<span class="mw-page-title-main">Buckminsterfullerene</span> Cage-like allotrope of carbon

Buckminsterfullerene is a type of fullerene with the formula C60. It has a cage-like fused-ring structure (truncated icosahedron) made of twenty hexagons and twelve pentagons, and resembles a soccer ball. Each of its 60 carbon atoms is bonded to its three neighbors.

<span class="mw-page-title-main">Metal carbonyl</span> Coordination complexes of transition metals with carbon monoxide ligands

Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry. In the Mond process, nickel tetracarbonyl is used to produce pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometallic complexes.

<span class="mw-page-title-main">Hapticity</span> Number of contiguous atoms in a ligand that bond to the central atom in a coordination complex

In coordination chemistry, 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.

The 18-electron rule is a chemical rule of thumb used primarily for predicting and rationalizing formulas for stable transition metal complexes, especially organometallic compounds. The rule is based on the fact that the valence orbitals in the electron configuration of transition metals consist of five (n−1)d orbitals, one ns orbital, and three np orbitals, where n is the principal quantum number. These orbitals can collectively accommodate 18 electrons as either bonding or non-bonding electron pairs. This means that the combination of these nine atomic orbitals with ligand orbitals creates nine molecular orbitals that are either metal-ligand bonding or non-bonding. When a metal complex has 18 valence electrons, it is said to have achieved the same electron configuration as the noble gas in the period, lending stability to the complex. Transition metal complexes that deviate from the rule are often interesting or useful because they tend to be more reactive. The rule is not helpful for complexes of metals that are not transition metals. The rule was first proposed by American chemist Irving Langmuir in 1921.

In organic chemistry, carbon–hydrogen bond functionalization is a type of organic reaction in which a carbon–hydrogen bond is cleaved and replaced with a C−X bond. The term usually implies that a transition metal is involved in the C−H cleavage process. Reactions classified by the term typically involve the hydrocarbon first to react with a metal catalyst to create an organometallic complex in which the hydrocarbon is coordinated to the inner-sphere of a metal, either via an intermediate "alkane or arene complex" or as a transition state leading to a "M−C" intermediate. The intermediate of this first step can then undergo subsequent reactions to produce the functionalized product. Important to this definition is the requirement that during the C−H cleavage event, the hydrocarbyl species remains associated in the inner-sphere and under the influence of "M".

<span class="mw-page-title-main">Fullerene chemistry</span>

Fullerene chemistry is a field of organic chemistry devoted to the chemical properties of fullerenes. Research in this field is driven by the need to functionalize fullerenes and tune their properties. For example, fullerene is notoriously insoluble and adding a suitable group can enhance solubility. By adding a polymerizable group, a fullerene polymer can be obtained. Functionalized fullerenes are divided into two classes: exohedral fullerenes with substituents outside the cage and endohedral fullerenes with trapped molecules inside the cage.

<span class="mw-page-title-main">Metallacycle</span>

In organometallic chemistry, a metallacycle is a derivative of a carbocyclic compound wherein a metal has replaced at least one carbon center; this is to some extent similar to heterocycles. Metallacycles appear frequently as reactive intermediates in catalysis, e.g. olefin metathesis and alkyne trimerization. In organic synthesis, directed ortho metalation is widely used for the functionalization of arene rings via C-H activation. One main effect that metallic atom substitution on a cyclic carbon compound is distorting the geometry due to the large size of typical metals.

Transition metal hydrides are chemical compounds containing a transition metal bonded to hydrogen. Most transition metals form hydride complexes and some are significant in various catalytic and synthetic reactions. The term "hydride" is used loosely: some of them are acidic (e.g., H2Fe(CO)4), whereas some others are hydridic, having H-like character (e.g., ZnH2).

Dioxygen complexes are coordination compounds that contain O2 as a ligand. The study of these compounds is inspired by oxygen-carrying proteins such as myoglobin, hemoglobin, hemerythrin, and hemocyanin. Several transition metals form complexes with O2, and many of these complexes form reversibly. The binding of O2 is the first step in many important phenomena, such as cellular respiration, corrosion, and industrial chemistry. The first synthetic oxygen complex was demonstrated in 1938 with cobalt(II) complex reversibly bound O2.

Organoplatinum chemistry is the chemistry of organometallic compounds containing a carbon to platinum chemical bond, and the study of platinum as a catalyst in organic reactions. Organoplatinum compounds exist in oxidation state 0 to IV, with oxidation state II most abundant. The general order in bond strength is Pt-C (sp) > Pt-O > Pt-N > Pt-C (sp3). Organoplatinum and organopalladium chemistry are similar, but organoplatinum compounds are more stable and therefore less useful as catalysts.

<span class="mw-page-title-main">Rhodocene</span> Organometallic 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 (302 °F) or when trapped by cooling to liquid nitrogen temperatures (−196 °C [−321 °F]). At room temperature, pairs of these radicals join via their cyclopentadienyl rings to form a dimer, a yellow solid.

In inorganic chemistry, the cis effect is defined as the labilization of CO ligands that are cis to other ligands. CO is a well-known strong pi-accepting ligand in organometallic chemistry that will labilize in the cis position when adjacent to ligands due to steric and electronic effects. The system most often studied for the cis effect is an octahedral complex M(CO)
5
X
where X is the ligand that will labilize a CO ligand cis to it. Unlike the trans effect, which is most often observed in 4-coordinate square planar complexes, the cis effect is observed in 6-coordinate octahedral transition metal complexes. It has been determined that ligands that are weak sigma donors and non-pi acceptors seem to have the strongest cis-labilizing effects. Therefore, the cis effect has the opposite trend of the trans-effect, which effectively labilizes ligands that are trans to strong pi accepting and sigma donating ligands.

<span class="mw-page-title-main">Transition metal benzyne complex</span>

Transition metal benzyne complexes are organometallic complexes that contain benzyne ligands (C6H4). Unlike benzyne itself, these complexes are less reactive although they undergo a number of insertion reactions.

In organometallic chemistry, a transition metal alkene complex is a coordination compound containing one or more alkene ligands. The inventory is large. Such compounds are intermediates in many catalytic reactions that convert alkenes to other organic products.

<span class="mw-page-title-main">Transition-metal allyl complex</span>

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.

Russell P. Hughes an American/British chemist, is the Frank R. Mori Professor Emeritus and Research Professor in the Department of Chemistry at Dartmouth College. His research interests are in organometallic chemistry, with emphasis on the chemistry of transition metal complexes interacting with fluorocarbons. His research group’s work in this area led to several creative syntheses of complexes of transition metal and perfluorinated hydrocarbon fragments.

Metal arene complexes are organometallic compounds of the formula (C6R6)xMLy. Common classes are of the type (C6R6)ML3 and (C6R6)2M. These compounds are reagents in inorganic and organic synthesis. The principles that describe arene complexes extend to related organic ligands such as many heterocycles (e.g. thiophene) and polycyclic aromatic compounds (e.g. naphthalene).

A transition metal phosphido complex is a coordination complex containing a phosphido ligand (R2P, where R = H, organic substituent). With two lone pairs on phosphorus, the phosphido anion (R2P) is comparable to an amido anion (R2N), except that the M-P distances are longer and the phosphorus atom is more sterically accessible. For these reasons, phosphido is often a bridging ligand. The -PH2 ion or ligand is also called phosphanide or phosphido ligand.

<span class="mw-page-title-main">Transition metal acyl complexes</span>

Transition metal acyl complexes describes organometallic complexes containing one or more acyl (RCO) ligands. Such compounds occur as transient intermediates in many industrially useful reactions, especially carbonylations.

<span class="mw-page-title-main">Transition metal azide complex</span>

Transition metal azide complexes are coordination complexes containing one or more azide (N3) ligands.

References

  1. Alan L. Balch; Joong W. Lee; Bruce C. Noll; Marilyn M. Olmstead (1994). "Multiple Additions of Vaska-Type Iridium Complexes to C60. Preferential Crystallization of the "Para" Double Addition Products: C60{Ir(CO)Cl(PMe3)2}2.2C6H6 and C60{Ir(CO)Cl(PEt3)2}2.C6H6". Inorg. Chem. 33: 5238–5243. doi:10.1021/ic00101a015.
  2. 1 2 3 Alan L. Balch; Marilyn M. Olmstead (1998). "Reactions of Transition Metal Complexes with Fullerenes (C60, C70, etc.) and Related Materials". Chem. Rev. 98 (6): 2123–2166. doi:10.1021/cr960040e. PMID   11848962.
  3. Krätschmer, W. (1990). "The infrared and ultraviolet absorption spectra of laboratory-produced carbon dust: evidence for the presence of the C60 molecule". Chemical Physics Letters. 170 (2–3): 167–170. Bibcode:1990CPL...170..167K. doi: 10.1016/0009-2614(90)87109-5 .
  4. Fagan, P.J.; Calabrese, J.C.; Malone, B. (1991). "The Chemical Nature of Buckminsterfullerene (C60) and the characterization of a platinum derivative". Science. 252 (5009): 1160–1161. Bibcode:1991Sci...252.1160F. doi:10.1126/science.252.5009.1160. ISSN   0036-8075. JSTOR   2876290. S2CID   95654230.
  5. 1 2 3 4 Denisovich, L. I.; Peregudova, S. M.; Novikov, Yu. N. (2010). "Electrochemical properties of transition metal complexes with C60 and C70 fullerene ligands (review)". Russian Journal of Electrochemistry. 46 (1): 1–17. doi:10.1134/S1023193510010015. S2CID   56103986.
  6. 1 2 Spessard, p. 162
  7. Spessard, p. 165
  8. Hsu, Hsiu-Fu; Shapley, John R. (1996). "Ru3(CO)93222-C60): A Cluster Face-Capping, Arene-Like Complex of C60". J. Am. Chem. Soc. 118 (38): 9192. doi:10.1021/ja962077m.
  9. Fagan, P.J.; Calabrese, J.C.; Malone, B. (1991). "A multiply-substituted buckminsterfullerene (C60) with an octahedral array of platinum atoms". Journal of the American Chemical Society. 113 (24): 9408–9409. doi:10.1021/ja00024a079.
  10. Toganoh, Motoki; Matsuo, Yutaka; Nakamura, Eiichi (2003). "Synthesis and catalytic activity of rhodium diene complexes bearing indenyl-type fullerene η5-ligand". Journal of Organometallic Chemistry. 683 (2): 295–300. doi:10.1016/S0022-328X(03)00465-0.
  11. RamíRez-Monroy, Armando; Swager, Timothy M. (2011). "Metal Chelates Based on Isoxazoline[60]fullerenes". Organometallics. 30 (9): 2464–2467. doi:10.1021/om200238a.
  12. Dragonetti, Claudia; Valore, Adriana; Colombo, Alessia; Righetto, Stefania; Rampinini, Giovanni; Colombo, Francesca; Rocchigiani, Luca; MacChioni, Alceo (2012). "An investigation on the second-order NLO properties of novel cationic cyclometallated Ir(III) complexes of the type [Ir(2-phenylpyridine)2(9-R-4,5-diazafluorene)]+ (R=H, fulleridene) and the related neutral complex with the new 9-fulleriden-4-monoazafluorene ligand". Inorganica Chimica Acta. 382: 72–78. doi:10.1016/j.ica.2011.10.018.
  13. Santos, Leandro J.; Carvalhoda-Silva, Dayse; Rebouças, Júlio S.; Alves, Marcos R.A.; Idemori, Ynara M.; Matencio, Tulio; Freitas, Rossimiriam P. (2011). "Synthesis of new porphyrin/fullerene supramolecular assemblies: A spectroscopic and electrochemical investigation of their coordination equilibrium in solution". Tetrahedron. 67: 228–235. doi:10.1016/j.tet.2010.10.066.

Bibliography