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]
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]
^ abMontgomery, 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: 308–309. 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. doi:10.1107/S0108270188011692.
^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.
^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.
January 01, 1970
dichlorobis, triphenylphosphine, nickel, refers, pair, metal, phosphine, complexes, with, formula, nicl2, c6h5, compound, exists, isomers, paramagnetic, dark, blue, solid, diamagnetic, solid, these, complexes, function, catalysts, organic, synthesis, dichlorob. 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 Dichlorobis triphenylphosphine nickel II Names IUPAC name dichloridobis triphenylphosphane nickel II Other names Bis triphenylphosphine nickel II dichlorideBis triphenylphosphine nickel II chlorideDichlorobis 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 c2 1 4 10 16 11 5 1 19 17 12 6 2 7 13 17 18 14 8 3 9 15 18 h2 1 15H 2 1H q 2 p 2Key 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 Contents 1 Synthesis and structure 2 Applications 3 See also 4 ReferencesSynthesis and structure editThe 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 A 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 A 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 editThe 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 nbsp A cross coupling reaction mediated by Ni cod 2 and Ni PPh3 2Cl2 9 See also editBis triphenylphosphine palladium II chloride Bis triphenylphosphine platinum II chlorideReferences edit 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 57 308 309 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 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 Joachim 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 Retrieved from https en wikipedia org w index php title Dichlorobis triphenylphosphine nickel II amp oldid 1206616513, wikipedia, wiki, book, books, library,
