Half sandwich compound

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Half sandwich compounds are organometallic complexes that feature a cyclic polyhapto ligand bound to an MLn center, where L is a unidentate ligand. Thousands of such complexes are known.[1][page needed] Well-known examples include cyclobutadieneiron tricarbonyl and (C5H5)TiCl3. Commercially useful examples include (C5H5)Co(CO)2, which is used in the synthesis of substituted pyridines, and methylcyclopentadienyl manganese tricarbonyl, an antiknock agent in petrol.

  • MMT is a commercially useful antiknock compound.

  • CpCo(CO)2 is a catalyst for the synthesis of pyridines.

  • (C4H4)Fe(CO)3.

  • CpFe(CO)2I is an example of an asymmetrical piano stool complex.

  • The diruthenium of cymene is readily cleaved by ligands to give monoRu half-sandwich derivatives.

  • Cp2V2(CO)5 featuring a pair of semi-bridging CO ligands.[2]

(η5-C5H5) piano stool compounds[]

Half sandwich complexes containing cyclopentadienyl ligands are common. Well studied examples include (η5-C5H5)V(CO)4, (η5-C5H5)Cr(CO)3H, (η5-CH3C5H4)Mn(CO)3, (η5-C5H5)Cr(CO)3H, [(η5-C5H5)Fe(CO)3]+, (η5-C5H5)V(CO)4I, and (η5-C5H5)Ru(NCMe)+
3. (η5-C5H5)Co(CO)2 is a two-legged piano stool complex. Bulky cyclopentadienyl ligands such as 1,2,4-C5H2(tert-Bu)3− form unusual half-sandwich complexes.[3]

(η6-C6H6) piano stool compounds[]

Piano Stool Complex.png

In organometallic chemistry, (η6-C6H6) piano stool compounds are half-sandwich compounds with (η6-C6H6)ML3 structure (M = Cr, Mo, W, Mn(I), Re(I) and L = typically CO). (η6-C6H6) piano stool complexes are stable 18-electron coordination compounds with a variety of chemical and material applications. Early studies on (η6-C6H6)Cr(CO)3 were carried out by Natta, Ercoli and Calderazzo,[4] and Fischer and Ofele,[5][6] and the crystal structure was determined by Corradini and Allegra in 1959.[7] The X-ray data indicate that the plane of the benzene ring is nearly parallel to the plane defined by the oxygen atoms of the carbonyl ligands, and so the structure resembles a benzene seat mounted on three carbonyl legs tethered by the metal atom.

Cr and Mn(I) (η6-C6H6) piano stool complexes[]

Piano stool complexes of the type (η6-C6H6)M(CO)3 are typically synthesized by heating the appropriate metal carbonyl compound with benzene. Alternately, the same compounds can be obtained by carbonylation of the bis(arene) sandwich compounds, such as (η6-C6H6)2M compound with the metal carbonyl compound. This second approach may be more appropriate for arene ligands containing thermally fragile substituents.[8]

Piano Synthesis 2.png

Reactivity of (η6-C6H6)Cr(CO)3[]

The benzene ligand in (η6-C6H6)Cr(CO)3Mi is prone to deprotonation.[9] For example, Organolithium compounds form adducts featuring cyclohexadienyl ligands. Subsequent oxidation of the complex results in the release of a substituted benzene.[10][11] Oxidation of the chromium atom by I2 and other iodine reagents has been shown to promote exchange of arene ligands, but the intermediate chromium iodide species has not been characterized.[12]

Arene-Cr(CO)3 Reaction with RLi.png

(η6-C6H6)Cr(CO)3 complexes exhibit "cine" and "tele" nucleophilic aromatic addition.[13] Processes of this type involve reaction of (η6-C6H6)Cr(CO)3 with an alkyl lithium reagent. Subsequent treatment with an acid results in the addition of a nucleophile to the benzene ring at a site ortho ("cine"), meta or para ("tele") to the ipso carbon (see Arene substitution patterns).

(Benzene)chromiumtricarbonyl electrophile nucleophilic carbonylation.png

Reflecting its increased acidity, the benzene ligand can be lithiated with n-butyllithium. The resulting organolithium compound serves as a nucleophile in various reactions, for example, with trimethylsilyl chloride:[citation needed]

(Benzene)chromiumtricarbonyl lithiation TMS.png

(η6-C6H6)Cr(CO)3 is a useful catalyst for the hydrogenation of 1,3-dienes. The product alkene results from 1,4-addition of hydrogen. The complex does not hydrogenate isolated double bonds.[citation needed]

A variety of arenes ligands have been installed aside from benzene.[14] Weakly coordinating ligands may be employed to improve ligand exchange and thus the turnover rates for (η6-C6H6)M(CO)3 complexes.[8]: 248 (η6-C6H6)M(CO)3 complexes have been incorporated into high surface area porous materials.[15]

(η6-C6H6)M(CO)3 complexes serve as models for the interaction of metal carbonyls with graphene and carbon nanotubes.[16] The presence of M(CO)3 on extended π-network materials has been shown to improve electrical conductivity across the material.[17]

Reactivity of [(η6-C6H6)Mn(CO)3]+[]

Typical arene tricarbonyl piano stool complexes of Mn(I) and Re(I) are cationic and thus exhibit enhanced reactivity toward nucleophiles. Subsequent to nucleophilic addition, the modified arene can be recovered from the metal.[18][19]

Mn Piano Stool Reaction.png

(η6-C6H6)Ru complexes[]

Half-sandwich compounds employing Ru(II), such as (cymene)ruthenium dichloride dimer, have been mainly investigated as catalysts for transfer hydrogenation.[20] These complexes feature three coordination sites that are susceptible to substitution, while the arene ligand is tightly bonded and protects the metal against oxidation to Ru(III). They are prepared by reaction of RuCl3·x(H2O) with 1,3-cyclohexadienes.[21] Work is also conducted on their potential as anticancer drugs.[22]

Synthesis of benzeneRu dimer2.png

(η6-C6H6)RuCl2 readily undergoes ligand exchange via cleavage of the chloride bridges, making this complex a versatile precursor to Ru(II) piano stool derivatives.[23]

References[]

  1. ^ Elschenbroich, C. (2006). Organometallics. Weinheim: Wiley-VCH. ISBN 978-3-527-29390-2.
  2. ^ Huffman, J. C.; Lewis, L. N.; Caulton, K. G. (1980). "A donor semibridge? Molecular structures of dicyclopentadienyldivanadiumtetracarbonyltriphenylphosphine and dicyclopentadienyldivanadiumpentacarbonyl". Inorganic Chemistry. 19 (9): 2755–2762. doi:10.1021/ic50211a052.
  3. ^ Reiners, Matthias; Ehrlich, Nico; Walter, Marc D. (2018). "Synthesis of 1,3,5-Tri-tert-Butylcyclopenta-1,3-diene and Its Metal Complexes Na{1,2,4-(Me3C)3C5H2} and Mg{η5-1,2,4-(Me3C)3C5H2)2". Inorganic Syntheses. 37: 199. doi:10.1002/9781119477822.ch8.
  4. ^ Natta, G.; Ercoli, R.; F., Calderazzo (1958). "(η-C6H6)Cr(CO)3". Chimica e Industria. 40: 1003.
  5. ^ Fischer, E. O.; Ofele, K.; Essler, H.; Frohlich, W.; Mortensen, J. P.; Semmlinger, W. (1958). "Über Aromatenkomplexe von Metallen. XXIV. Über gemischte Tricarbonylkomplexe des Chroms, Molybdäns und Wolframs mit Benzol und seinen Derivaten" [On aromatic complexes of metals. 24. On mixed tricarbonyl complexes of chromium, molybdenum and tungsten with benzene and its derivatives]. Chemische Berichte. 91 (12): 2763–2772. doi:10.1002/cber.19580911231.
  6. ^ Fischer, E. O.; Ofele, K. (1957). "Über Aromatenkomplexe von Metallen. XIII. Benzol‐Chrom‐Tricarbonyl" [On aromatic complexes of metals. 13. Benzene chromium tricarbonyl]. Chemische Berichte. 90 (11): 2532–2535. doi:10.1002/cber.19570901117.
  7. ^ Corradini, P.; Allegra, G. (1959). "X-ray determination of the structure of tricarbonylchromium-benzene". Journal of the American Chemical Society. 81 (9): 2271–2272. doi:10.1021/ja01518a065.
  8. ^ Jump up to: a b Hartwig, John (2010). Organotransition Metal Chemistry. Sausalito: University Science Books. p. 443. ISBN 978-1-891389-53-5.
  9. ^ Crabtree, R. (2009). The Organometallic Chemistry of Transition Metals (5th ed.). Hoboken, NJ: John Wiley & Sons. p. 145. ISBN 978-0-470-25762-3.
  10. ^ A., Didier (2007). Organometallic Chemistry and Catalysis. Berlin: Springer-Verlag. pp. 243–246. ISBN 978-3-540-46128-9.
  11. ^ Herndon, J. W.; Laurent, S. E. (2008). "(η6-Benzene)tricarbonylchromium". Encyclopedia of Reagents for Organic Synthesis. Chichester: John Wiley & Sons. doi:10.1002/047084289X.rb025.pub2.
  12. ^ Harrison, J. J. (1984). "Iodine-catalyzed arene exchange of (arene)tricarbonyl chromium(0) complexes". Journal of the American Chemical Society. 106 (5): 1487–1489. doi:10.1021/ja00317a052.
  13. ^ Djukic, J.-P.; Rose-Munch, F.; Rose, E.; Simon, F.; Dromzee, Y. (1995). "Nucleophilic aromatic substitutions: hydrodealkoxylation, hydrodehalogenation, and hydrodeamination of alkoxy, halogeno, and amino (η6-arene)tricarbonylchromium complexes". Organometallics. 14 (4): 2027–2038. doi:10.1021/om00004a065.
  14. ^ Clark, I. P.; George, M. W.; Greetham, G. M.; Harvey, E. C.; Long, C.; Manton, J. C.; Pryce, M. T. (2011). "Photochemistry of (η6-arene)Cr(CO)3 (arene = methylbenzoate, naphthalene, or phenanthreen) in n-heptane solution: Population of two excited states following 400 nm excitation as detected by picosecond time-resolved infrared spectroscopy". Journal of Physical Chemistry A. 115 (14): 2985–2993. Bibcode:2011JPCA..115.2985C. doi:10.1021/jp112168u.
  15. ^ Kamegawa, T.; Saito, M.; Sakai, T.; Matsuoka, M.; Anpo, M. (2012). "Characterization of phenylene-bridged hybrid mesoporous materials incorporating arenetricarbonyl complexes (-C6H4Me(CO)3-; Me = Cr, Mo) and their catalytic activities". Catalysis Today. 181 (1): 14–19. doi:10.1016/j.cattod.2011.10.019.
  16. ^ Duncan, M. A. (2008). "Structures, energetics and spectroscopy of gas phase transition metal ion-benzene complexes". International Journal of Mass Spectrometry. 272 (2–3): 99–118. Bibcode:2008IJMSp.272...99D. doi:10.1016/j.ijms.2008.01.010.
  17. ^ Kalinina, Irina; Bekyarova, E.; Sarkar, S.; Wang, F.; Itkis, M.; Tian, X.; Niyogi, S.; Jha, N.; Haddon, R. C. (2012). "Hexahapto-metal carbonyl complexes of single walled carbon nanotubes". Macromolecular Chemistry and Physics. 213 (3–4): 1001–1019. doi:10.1016/j.ccr.2008.04.014.
  18. ^ Walker, P. J. C.; Mawby, R. J. (1973). "Patterns of nucleophilic attack on tricarbonyl pi-arene complexes of manganese(I)". Inorganica Chimica Acta. 7: 621–625. doi:10.1016/s0020-1693(00)94897-7.
  19. ^ Brookhart, M.; Pinhas, A. R.; Lukacs, A. (1982). "Reaction of lithium dimethyl cuprate with C6H6Mn(CO)3. Observation of methyl group migration from manganese to arene ring in C6H6(CO)2MnMe". Organometallics. 1 (12): 1730–1731. doi:10.1021/om00072a040.
  20. ^ Ikariya, T.; Blacker, A. J. (2007). "Asymmetric Transfer Hydrogenation of Ketones with Bifunctional Transition Metal-Based Molecular Catalysts". Accounts of Chemical Research. 40: 1300–1308. doi:10.1021/ar700134q. PMID 17960897.
  21. ^ Bennett, M. A.; Huang, T. N.; Matheson, T. W.; Smith, A. K. (1982). "(η6-Hexamethylbenzene)ruthenium Complexes". Inorganic Syntheses. 21: 74–78. doi:10.1002/9780470132524.ch16.
  22. ^ Bruijnincx, P. C. A.; Sadler, P. J. (2009). Controlling platinum, ruthenium, and osmium reactivity for anticancer drug design. Advances in Inorganic Chemistry. 61. pp. 1–62. doi:10.1016/S0898-8838(09)00201-3. ISBN 9780123750334. PMC 3024542. PMID 21258628.
  23. ^ Therrien, B. (2009). "Functionalised η6-arene ruthenium complexes". Coordination Chemistry Reviews. 253 (3–4): 493–519. doi:10.1016/j.ccr.2008.04.014.

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