Dichlorobis(triphenylphosphine)nickel(II)

Dichlorobis(triphenylphosphine)nickel(II)
Names
	IUPAC name dichloridobis(triphenylphosphane)nickel(II)
	Other names Bis(triphenylphosphine)nickel(II) dichloride; Bis(triphenylphosphine)nickel(II) chloride; Dichlorobis(triphenylphosphine)nickel(II); Bis(triphenylphosphine)nickel chloride
Identifiers
CAS Number	39716-73-9 (tetrahedral form); 14264-16-5 (square planar form);
3D model (JSmol)	Interactive image;
ChemSpider	76051;
EC Number	238-154-8;
PubChem CID	498315;
	InChI InChI=1S/2C18H15P.2ClH.Ni/c21-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;/h21-15H;2*1H;/q;;;;+2/p-2 Key: ZBRJXVVKPBZPAN-UHFFFAOYSA-L;
	SMILES C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=CC=CC=C3.C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=CC=CC=C3.Cl[Ni]Cl;
Properties
Chemical formula	C36H30Cl2NiP2
Appearance	purple-blue (tetrahedral) or red (sq. planar)
Hazards
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H302, H317, H350, H412
Precautionary statements	P201, P202, P261, P264, P270, P272, P273, P280, P281, P301+P312, P302+P352, P308+P313, P321, P330, P333+P313, P363, P405, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Dichlorobis(triphenylphosphine)nickel(II) refers to a pair of metal phosphine complexes with the formula NiCl₂[P(C₆H₅)₃]₂. The compound exists as two isomers, a paramagnetic dark blue solid and a diamagnetic red solid. These complexes function as catalysts for organic synthesis.^[1]

Synthesis and structure

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] Dichlorobis(triphenylphosphine)nickel(II) is a catalyst in Suzuki reactions, although usually inferior in terms of activity.^[8]

References

^ ^a ^b Montgomery, J. Science of Synthesis Georg Thiene Verlag KG, Vol. 1, p 11, CODEN: SSCYJ9
^ Batsanov, Andrei S.; Howard, Judith A. K. (2001). "trans-Dichlorobis(triphenylphosphine)nickel(II) bis(dichloromethane) solvate: redetermination at 120 K". Acta Crystallogr E. 57 (7): 308–309. Bibcode:2001AcCrE..57M.308B. doi:10.1107/S1600536801008741. S2CID 97381117.
^ 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.
^ Garton, G.; Henn, D. E.; Powell, H. M.; Venanzi, L. M. (1963). "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.
^ Brammer, L.; Stevens, E. D. (1989). "Structure of dichlorobis(triphenylphosphine)nickel(II)". Acta Crystallogr C. 45 (3): 400–403. Bibcode:1989AcCrC..45..400B. doi:10.1107/S0108270188011692.
^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
^ Reppe, Walter; Sweckendiek, Walter (1948). "Cyclisierende Polymerisation von Acetylen. III Benzol, Benzolderivate und hydroaromatische Verbindungen". Justus Liebigs Annalen der Chemie. 560 (1): 104–16. doi:10.1002/jlac.19485600104.
^ 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.
^ Johnson, Jeffrey S.; Berman, Ashley M. (2005-07-01). "Nickel-Catalyzed Electrophilic Amination of Organozinc Halides". Synlett. 2005 (11): 1799–1801. doi:10.1055/s-2005-871567.
^ Quasdorf, Kyle W.; Garg, Neil K. (2010). "Bis(tricyclohexylphosphine)dichloronickel". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rn01201. ISBN 978-0-471-93623-7.

[Montgomery_Synthesis-1] 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 (7): 308–309. Bibcode:2001AcCrE..57M.308B. doi:10.1107/S1600536801008741. S2CID 97381117.

[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. (1963). "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. Bibcode:1989AcCrC..45..400B. doi:10.1107/S0108270188011692.

[6] Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.

[7] Reppe, Walter; Sweckendiek, Walter (1948). "Cyclisierende Polymerisation von Acetylen. III Benzol, Benzolderivate und hydroaromatische Verbindungen". 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.

[9] Johnson, Jeffrey S.; Berman, Ashley M. (2005-07-01). "Nickel-Catalyzed Electrophilic Amination of Organozinc Halides". Synlett. 2005 (11): 1799–1801. doi:10.1055/s-2005-871567.

[10] Quasdorf, Kyle W.; Garg, Neil K. (2010). "Bis(tricyclohexylphosphine)dichloronickel". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rn01201. ISBN 978-0-471-93623-7.

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Dichlorobis(triphenylphosphine)nickel(II)

Synthesis and structure

Applications

See also

References

Information related to Dichlorobis(triphenylphosphine)nickel(II)

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