Sandwich compound

units.

The term "sandwich compound" was introduced in organometallic nomenclature in during the mid-1950s when J.D. Dunitz, L.E. Orgel and R.A. Rich confirmed the structure of ferrocene by X-ray crystallography. [cite journal | author = J. Dunitz, L. Orgel, A. Rich | title = The crystal structure of ferrocene | journal = Acta Crystallographica | year = 1956 | volume = 9 | pages = 373–5 | doi = 10.1107/S0365110X56001091] The correct structure had been proposed several years previously by Robert Burns Woodward. Of particular interest, the structure helped explain puzzles about ferrocene's conformers, the molecule features an iron atom "sandwiched" between two parallel cyclopentadienyl rings. This result further demonstrated the power of X-ray crystallography, accelerating the growth of organometallic chemistry. [cite book | last = Miessler | first = Gary L. | authorlink = Gary L. Miessler | coauthors = Donald A. Tarr | year = 2004 | title = Inorganic Chemistry | publisher = Pearson Education, Inc. Pearson Prentice Hall | location = Upper Saddle River, New Jersey | id = ISBN 0-13-035471-6]

Classes of sandwich compounds

The best known members are the metallocenes of the formula M(C₅H₅)₂ where M = Cr, Fe, Co, Ni, Zr, Ti, V, Mo, W, Zn. These species are also called Bis(cyclopentadienyl)metal complexes.
*Mixed cyclopentadienyl complexes: M(C₅H₅)(C_nH_n). An example is Ti(C₅H₅)(C₇H₇)
*Bis(benzene) complexes: M(C₆H₆)₂, the best known example being Bis(benzene)chromium.
*Bis(cyclooctatetraenyl) complexes: U(C₈H₈)₂, the Th derivative is also known.

Sandwich complexes are even known containing purely inorganic ligands, such as Fe(C₅Me₅)(P₅) and [(P₅)₂Ti] ^2-. [cite journal| author = Urnezius, E.; Brennessel, W. W.; Cramer, C. J.; Ellis, J. E. and von Rague Schleyer, P. | title = A Carbon-Free Sandwich Complex [(P₅)₂Ti] ^2- | journal = Science | year = 2002 | volume = 295 | pages = 832–834 | doi = 10.1126/science.1067325| pmid = 11823635]

Half sandwich compounds

Monometallic half sandwich compounds

Metallocenes including just one facially-bound planar organic ligand instead of two gives rise to a still larger family of "half sandwich" compounds. The most famous example is probably methylcyclopentadienyl manganese tricarbonyl. Such species are occasionally referred to "piano stool" compounds, at least when there are three diatomic ligands in addition to the hydrocarbon "seat" of the piano stool. The name derives from the similarity of the structure to such a "stool" with the seat being a facial planar organic compound, e.g. benzene or cyclopentadiene, and the legs being ligands such as CO or allyl.

Dimetallic half sandwich compounds

Compounds such as the cyclopentadienyliron dicarbonyl dimer and cyclopentadienylmolybdenumtricarbonyl dimer can be considered a special case of half-sandwiches, except that they are dimetallic. A structurally related species is [Ru(C₆H₆)Cl₂] ₂.

Multimetallic sandwich compounds

The compound depicted below has four palladium atoms joined in a chain sandwiched between two perylene units. [cite journal | title = Perylene-Tetrapalladium Sandwich Complexes | author = Tetsuro Murahashi, Tomohito Uemura, and Hideo Kurosawa | journal = J. Am. Chem. Soc. | year = 2003 | volume = 125 | issue = 28 | pages = 8436–8437 | format = Communication | doi = 10.1021/ja0358246] The counterions are bulky tetraarylborates.

Multidecker sandwiches

The first multidecker sandwich complex was the dicationic triscyclopentadienyl dinickel complex [Ni₂Cp₃] (BF₄)₂. This motif has been replicated many times, especially by attachment of Cp*Ru⁺ to preformed sandwich complexes. [cite journal | author = Fagan, P. J.; Ward, M. D.; Calabrese, J. C. | title = Molecular engineering of solid-state materials: organometallic building blocks | journal = J. Am. Chem. Soc. | year = 1989 | volume = 111 | pages = 1698–719 | doi = 10.1021/ja00187a024]

References