Dihydrogen complex
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Formation and equilibrium structures of metal dihydrogen and dihydride complexes (L = ligand).
Formation and equilibrium structures of metal dihydrogen and dihydride complexes (L = ligand).

Dihydrogen complexes are coordination complexes containing intact H2 as a ligand.[1] The prototypical complex is W(CO)3(P(Cy)3)2(H2). This class of compounds represent intermediates in metal-catalyzed reactions involving hydrogen. Hundreds of dihydrogen complexes have been reported. Most examples are cationic transition metals complexes with octahedral geometry.

Upon complexation, the H-H bond is extended to 0.81-0.82 Å as indicated by neutron diffraction, about a 10% extension relative to the H-H bond in free H2. Some complexes containing multiple hydrogen ligands, i.e. polyhydrides, also exhibit short H---H contacts. It has been suggested that distances < 1.00 Å indicates signficant dihydrogen character, where separations > 1 Å are better described as dihydrido complexes (see figure).

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Characterization

The preferred method of characterization of dihydrogen complexes is neutron diffraction. Neutrons interact strongly with hydrogen atoms, which allows one to infer their location in a crystal. In some cases, hydrogen ligands are usefully characterized by X-ray crystallography, but often the presence of metals, which strongly scatter X-rays, complicates the analysis. NMR techniques are also widely used. The magnitude of spin-spin coupling is a useful indicator of the strength of the bond between the hydrogen and deuterium in HD complexes. Dihydrogen-complexes typically have longer 1H-spin-lattice relaxation times than the corresponding dihydrides.

Synthesis

Two preparation methods involve the direct reactions with H2 gas. The first entails the addition of H2 to an unsaturated metal center, as originally reported for W(CO)3(P-i-Pr3)2(H2). In some cases, H2 will displace weakly bound ligands, sometimes even halides in favorable cases:

LnMX + H2 → [LnM(H2)]+ + X-

Many metal hydrides can be protonated to give dihydrogen complexes:

LnM-H + H+ → [LnM(H2)]+

In such cases the acid usually is derived from a weakly coordinating anion.

History

In 1984, Kubas et al. discovered that the addition of H2 to purple-colored species M(CO)3(PR3)2 gave a yellow precipitate of mer-trans- M(CO)3(PR3)2(H2) (M = Mo or W; R = cyclohexyl, iso-propyl).[2] This result rapidly led to the discovery of a variety of related complexes such as Cr(H2)(CO)5[3] and [Fe(H2)(H)(dppe)2+.[4] Kubas et al's findings also led to a reevaluation of previously described compounds. For example, the complex "RuH4(PPh3)3" described in 1968 was reformulated as a dihydrogen complex.

References

  1. ^ Kubas, G. J., "Metal Dihydrogen and σ-Bond Complexes", Kluwer Academic/Plenum Publishers: New York, 2001. ISBN 0-306-46465-9
  2. ^ Kubas, G. J.; Ryan, R. R.; Swanson, B. I.; Vergamini, P. J.; Wasserman, H. J. "Characterization of the First Examples of Isolable Molecular Hydrogen Complexes, M( CO)3(PR3)2(H2) (M = Mo, W; R = Cy, i-Pr). Evidence for a Side-on Bonded H2 Ligand" Journal of the American Chemical Society 1984, volume 100, 451-2.
  3. ^ Sweany, R. L. "Photolysis of Hexacarbonylchromium in Hydrogen-Containing matrixes: evidence of simple adducts of molecular hydrogen" Journal of the American Chemical Society 1985, volume 107, 2374-9. DOI: 10.1021/ja00294a030
  4. ^ Morris, R. H.; Sawyer, J. F.; Shiralian, M. and Zubkowski, J., "Two Molecular Hydrogen Complexes: trans-[M(η2-H2)(H)(PPh2CH2CH2PPh2)2]BF4 (M = Fe, Ru). The Crystal Structure Determination of the Iron Complex", Journal of the American Chemical Society, 1985, volume 107, 5581-2.{DOI|10.1021/ja00305a071}

1 # Kubas, G. J., "Metal Dihydrogen and σ-Bond Complexes", Kluwer Academic/Plenum Publishers: New York, 2001. ISBN 0-306-46465-9

2 ^ Kubas, G. J.; Ryan, R. R.; Swanson, B. I.; Vergamini, P. J.; Wasserman, H. J. "Characterization of the First Examples of Isolable Molecular Hydrogen Complexes, M( CO)3(PR3)2(H2) (M = Mo, W; R = Cy, i-Pr). Evidence for a Side-on Bonded H2 Ligand" Journal of the American Chemical Society 1984, volume 106, 451-2

3 ^ Sweany, R. L. "Photolysis of Hexacarbonylchromium in Hydrogen-Containing matrixes: evidence of simple adducts of molecular hydrogen" Journal of the American Chemical Society 1985, volume 107, 2374-9. DOI: 10.1021/ja00294a030

4 ^ Morris, R. H.; Sawyer, J. F.; Shiralian, M. and Zubkowski, J., "Two Molecular Hydrogen Complexes: trans-[M(η2-H2)(H)(PPh2CH2CH2PPh2)2]BF4 (M = Fe, Ru). The Crystal Structure Determination of the Iron Complex", Journal of the American Chemical Society, 1985, volume 107, 5581-2.{DOI|10.1021/ja00305a071}

Further reading

  1. J. K. Burdett, O. Eisenstein, and S. A. Jackson, “Transition Metal Didydrogen Complexes: Theoretical Studies,” in A. Dedieu,

ed., Transition Metal Hydrides, VCH, New York, 1992, pp. 149-184

  1. Burdett, J. K.; Phillips, J. R.; Pourian, M. R.; Poliakoff, M.; Turner, J. J.; Upmacis, R. K. Inorg. Chem. 1987, 26, 3054
  2. Lyons, D.; Wilkinson, G..; Thornton-Pett, M.; Hursthouse, M. B. J. Chem. Soc., Dalton Trans. 1986, 695
  3. Kubas, G. J.; Ryan, R. R. Polyhedron 1986, 5, 473
  4. Crabtree, R. H.; Lavin, M. J. Chem. Soc.; Chem. Commun. 1985, 1661.
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Chemical bonds
"Strong"
-
"Weak"
other
Note: the weakest strong bonds are not necessarily stronger than the strongest weak bonds
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