Dichloridobis(triphenylphosphane)nickel(II)

Dichloridobis(triphenylphosphane)nickel(II)
Names
IUPAC name
dichloridobis(triphenylphosphine)nickel(II)
Other names
Bis(triphenylphosphine)nickel(II) dichloride
Bis(triphenylphosphine)nickel(II) chloride
Dichlorobis(triphenylphosphine)nickel(II)
Bis(triphenylphosphine)nickel chloride
Identifiers
(tetrahedral form) 14264-16-5 (square planar form) 39716-73-9 (tetrahedral form) 14264-16-5 (square planar form)
Properties
C36H30Cl2NiP2
Appearance purple-blue (tetrahedral) or red (sq. planar)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Dichloridobis(triphenylphosphine)nickel(II) is a metal phosphine complex with the formula NiCl2[P(C6H5)3]2. It is a dark blue crystalline solid. It is used as a catalyst for organic synthesis.[1]

Synthesis and structure

Dichloridobis(triphenylphosphine)nickel(II) is a commercially available reagent. The blue isomer is prepared by treating hydrated nickel chloride with triphenylphosphine in alcohols or glacial acetic acid:[1]

NiCl2•6H2O + 2 PPh3 → NiCl2(PPh3)2 + 6 H2O

When allowed to crystallise from chlorinated solvents, the tetrahedral isomer converts to the square planar isomer.

The square planar form is red and diamagnetic. The phosphine ligands are trans with respective Ni-P and Ni-Cl distances of 2.24 and 2.17 Å.[2][3] The blue form is paramagnetic and features tetrahedral Ni(II) centers. In this isomer, the Ni-P and Ni-Cl distances are elongated at 2.32 and 2.21 Å.[4][5]

As illustrated by the title complexes, tetrahedral and square planar isomers coexist in solutions of various four-coordinated nickel(II) complexes. Weak field ligands, as judged by the spectrochemical series, favor tetrahedral geometry and strong field ligands favor the square planar isomer. Both weak field (Cl−) and strong field (PPh3) ligands comprise NiCl2(PPh3)2, hence this compound is borderline between the two geometries. Steric effects also affect the equilibrium; larger ligands favoring the less crowded tetrahedral geometry.[6]

Applications

The complex was first described by Walter Reppe who popularized its use in alkyne trimerisations and carbonylations.[7] Dichloridobis(triphenylphosphane)nickel(II) is a catalyst in Suzuki reactions as an alternative to the traditional palladium(0) catalysts because nickel is cheaper and more abundant. It is not a full substitute since nickel has different catalytic properties than palladium.[8]

References

  1. 1 2 Montgomery, J. Science of Synthesis Georg Thiene Verlag KG, Vol. 1, p 11, CODEN: SSCYJ9
  2. ↑ Batsanov, Andrei S.; Howard, Judith A. K. (2001). "trans-Dichlorobis(triphenylphosphine)nickel(II) bis(dichloromethane) solvate: redetermination at 120 K". Acta Crystallogr E. 57: 308–309. doi:10.1107/S1600536801008741.
  3. ↑ Corain, B.; Longato, B.; Angeletti, R.; Valle, G. (1985). "trans:-[Dichlorobis(triphenylphosphine)nickel(II)]·(C2H4Cl2)2 a clathrate of the allogon of venanzi's tetrahedral complex". Inorg. Chim. Acta. 104: 15–18. doi:10.1016/S0020-1693(00)83780-9.
  4. ↑ Garton, G.; Henn, D. E.; Powell, H. M.; Venanzi, L. M. "Tetrahedral nickel(II) complexes and the factors determining their formation. Part V. The tetrahedral co-ordination of nickel in dichlorobistriphenylphosphinenickel". J. Chem. Soc. 1963: 3625–3629. doi:10.1039/JR9630003625.
  5. ↑ Brammer, L.; Stevens, E. D. (1989). "Structure of dichlorobis(triphenylphosphine)nickel(II)". Acta Crystallogr C. 45 (3): 400–403. doi:10.1107/S0108270188011692.
  6. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9.
  7. ↑ Reppe, Walter; Sweckendiek, Walter (1948). "Cyclisierende Polymerisation von Acetylen. III Benzol, Benzolderivate und hydroaromatische Verbindungen". Joachim Justus Liebigs Annalen der Chemie. 560 (1): 104–16. doi:10.1002/jlac.19485600104.
  8. ↑ Han, Fu-She (2013). "Transition-metal-catalyzed Suzuki–Miyaura cross-coupling reactions: A remarkable advance from palladium to nickel catalysts". Chemical Society Reviews. 42 (12): 5270–98. doi:10.1039/c3cs35521g. PMID 23460083.
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