Organoruthenium chemistry

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Organoruthenium chemistry is the chemistry of organometallic compounds containing a carbon to ruthenium chemical bond.1 The interest is mostly academic although several organoruthenium catalysts are of commercial interest. The chemistry has some stoichiometric similarities with organoiron chemistry, as iron is directly above ruthenium in group 8 of the periodic table. The most important reagents for the introduction of ruthenium are ruthenium(III) chloride and triruthenium dodecacarbonyl.

In its organometallic compounds, ruthenium is known to adopt oxidation states from -2 ([Ru(CO)42-) to +6 ([RuN(Me)4]-). Most common are those in the 2+ oxidation state, as illustrated below.

Ligands

As with other late transition metals, ruthenium binds more favorably with soft ligands.2 The most important ligands for ruthenium are:

Phosphine ligands

While monodentate phosphine ligands such as triphenyphosphine and tricyclohexylphosphine are most common, bidentate phosphine ligands can also be useful in organoruthenium compounds. BINAP, in particular, is a useful asymmetric ligand for many asymmetric ruthenium catalysts.3456

N-Heterocyclic carbene ligands

NHC ligands have become very common in organoruthenium complexes.78 NHC ligands can be prepared with precise steric and electronic parameters, and can be chiral for use in asymmetric catalysis.9 NHCs, as strongly donating L-type ligands, are often used to replace phosphine ligands. A notable example is 2nd generation Grubbs' catalyst, in which a phosphine of the 1st generation catalyst is replaced by an NHC.

Cyclopentadienyl ligands

The parent compound ruthenocene is unreactive because it is coordinatively saturated and contains no reactive groups. Shvo's catalyst ([Ph45-C4CO)]2H]}Ru2(CO)4(μ-H)) is also coordinatively saturated, but features reactive OH and RuH groups that enable it to function in transfer hydrogenation.10 It is used in hydrogenation of aldehydes, ketones, via transfer hydrogenation, in disproportionation of aldehydes to esters and in the isomerization of allylic alcohols.

Chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium features a reactive chloro group, which is readily substituted by organic substrates.

Arene and alkene ligands

One example of an Ru-arene complex is (cymene)ruthenium dichloride dimer, which is the precursor to a versatile catalyst for transfer hydrogenation.11 Acenaphthylene forms a useful catalyst derived from triruthenium dodecacarbonyl.12 The hapticity of the hexamethylbenzene ligand in Ru(C6Me6)2 depends on the oxidation state of the metal centre (methyl groups omitted for clarity):13

Ru(C6H6)2redox.png

The compound Ru(COD)(COT) is capable of dimerizing norbornadiene:

Norbornadiene dimerization

Carbonyls

The main ruthenium carbonyl is triruthenium dodecacarbonyl, Ru3(CO)12. The analogues of the popular reagents Fe(CO)5 and Fe2(CO)9 are not very useful. The pentacarbonyl de[carbonylate]]s readily:

Ru3(CO)12 + 3 CO \overrightarrow{\leftarrow} 3 Ru(CO)5

Carbonylation of ruthenium trichloride gives a series of Ru(II) chlorocarbonyls. These are the precursors to Ru3(CO)12.

Organoosmium compounds

In the same group 8 elements osmium resembles ruthenium in its complexes. Because Os is more expensive than Ru, the chemistry is less developed and has fewer applications. Of course the cost of the catalyst is offset if turnover numbers are high. Thus, Osmium tetroxide is an important oxidizing agent in organic chemistry especially in the conversion of alkenes to 1,2-diols.

The 5d-orbitals in Os are higher in energy that the 4d-orbitals in Ru. Thus, π backbonding to alkenes and CO is stronger for Os compounds, which leads to more stable organic derivatives. This effect is illustrated by the stability of the alkene derivatives of the type [Os(NH3)5(alkene)]2+ or [Os(NH3)5(arene)]2+ as in the example below.

OsA5(eta-2-benzene).png

Important compounds, at least for academic studies, are the carbonyls such as triosmium dodecacarbonyl and decacarbonyldihydridotriosmium. The phosphine complexes are analogous to those or ruthenium, but hydride derivatives, e.g. OsHCl(CO)(PPh3)3, tend to be more stable.

See also

  • Chemical bonds of carbon with other elements in the periodic table:
CH He
CLi CBe CB CC CN CO CF Ne
CNa CMg CAl CSi CP CS CCl CAr
CK CCa CSc CTi CV CCr CMn CFe CCo CNi CCu CZn CGa CGe CAs CSe CBr CKr
CRb CSr CY CZr CNb CMo CTc CRu CRh CPd CAg CCd CIn CSn CSb CTe CI CXe
CCs CBa CHf CTa CW CRe COs CIr CPt CAu CHg CTl CPb CBi CPo CAt Rn
Fr CRa Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo
CLa CCe CPr CNd CPm CSm CEu CGd CTb CDy CHo CEr CTm CYb CLu
Ac CTh CPa CU CNp CPu CAm CCm CBk CCf CEs Fm Md No Lr
Chemical bonds to carbon
Core organic chemistry Many uses in chemistry
Academic research, but no widespread use Bond unknown

References

  1. ^ Synthesis of Organometallic Compounds: A Practical Guide Sanshiro Komiya Ed. S. Komiya, M. Hurano 1997
  2. ^ Barthazy, P.; Stoop, R. M.; Wörle, M.; Togni, A.; Mezzetti, A. (2000). "Toward Metal-Mediated C-F Bond Formation. Synthesis and Reactivity of the 16-Electron Fluoro Complex [RuF(dppp)2PF6 (dppp = 1,3-Bis(diphenylphosphino)propane)". Organometallics 19: 2844–2852. doi:10.1021/om0000156. 
  3. ^ Example: Organic Syntheses, Coll. Vol. 10, p.276 (2004); Vol. 77, p.1 (2000). Link
  4. ^ Example: Organic Syntheses, Organic Syntheses, Coll. Vol. 9, p.589 (1998); Vol. 71, p.1 (1993). Link
  5. ^ Example: Organic Syntheses, Organic Syntheses, Coll. Vol. 9, p.169 (1998); Vol. 72, p.74 (1995). Link
  6. ^ Example: Organic Syntheses, Vol. 81, p.178 (2005). Link
  7. ^ Öfele, K.; Tosh, E.; Taubmann, C.; Herrmann, W.A. (2009). "Carbocyclic Carbene Metal Complexes". Chemical Reviews 109 (8): 3408–3444. doi:10.1021/cr800516g. 
  8. ^ Samojłowicz, C.; Bieniek, M.; Grela, K. (2009). "Ruthenium-Based Olefin Metathesis Catalysts Bearing N-Heterocyclic Carbene Ligands". Chemical Reviews 109 (8): 3708–3742. doi:10.1021/cr800524f. PMID 19534492. 
  9. ^ Benhamou, L.; Chardon, E.; Lavigne, G.; Bellemin-Laponnaz, S.; César, V. (2011). "Synthetic Routes to N-Heterocyclic Carbene Precursors". Chemical Reviews 111 (12). doi:10.1021/cr100328e. 
  10. ^ Conley, B.; Pennington-Boggio, M.; Boz, E.; Williams, T. (2010). "Discovery, Applications, and Catalytic Mechanisms of Shvo's Catalyst". Chemical reviews 110 (4): 2294–2312. doi:10.1021/cr9003133. PMID 20095576. 
  11. ^ Organic Syntheses, Organic Syntheses, Vol. 82, p.10 (2005).Link
  12. ^ Example: Organic Syntheses, Organic Syntheses, Vol. 82, p.188 (2005). Link
  13. ^ Huttner, Gottfried; Lange, Siegfried; Fischer, Ernst O. (1971). "Molecular Structure of Bis(Hexamethylbenzene)-Ruthenium(0)". Angewandte Chemie, International Edition in English 10 (8): 556–557. doi:10.1002/anie.197105561.