Triphos

Triphos is the name for certain organophosphorus ligands. They are air-sensitive white solids that function as tridentate ligands in coordination and organometallic chemistry.

Triphos
Names
IUPAC name
Bis(diphenylphosphinoethyl)phenylphosphine
Other names
Triphos
Identifiers
3D model (JSmol)
ChemSpider
Properties
C34H29P3
Molar mass 534.55 g/mol
Appearance white crystals
Melting point 129 to 130 °C (264 to 266 °F; 402 to 403 K)
Insoluble
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
Triphos
Names
IUPAC name
1,1,1-Tris(diphenylphosphinomethyl)ethane
Other names
Triphos,
tdppme,
tdme
Identifiers
3D model (JSmol)
ChemSpider
Properties
C41H39P3
Molar mass 624.67 g/mol
Appearance white crystals
Melting point 99 to 102 °C (210 to 216 °F; 372 to 375 K)
Insoluble
Hazards
Safety data sheet Triphos MSDS
S-phrases (outdated) 22-24/25
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Bis(diphenylphosphinoethyl)phenylphosphine

Bis(diphenylphosphinoethyl)phenylphosphine is called triphos, is a linear tridentate triphosphine. It is prepared by the free-radical-catalysed addition of phenylphosphine to vinyldiphenylphosphine:[1]

2 Ph2PCH=CH2 + H2PPh → [Ph2PCH2CH2]2PPh

This isomer of triphos is flexible and can bind to an octahedral metal center give either a facial or meridional isomers. Some derivatives are square planar complexes of the type [MX(triphos)]+ (M = Ni, Pd, Pt; X = halide).

1,1,1-Tris(diphenylphosphinomethyl)ethane

1,1,1-Tris(diphenylphosphinomethyl)ethane is also called triphos. It is a tripodal ligand ("three-legged") of idealized C3v symmetry. It was originally prepared by the reaction of sodium diphenylphosphide and CH3C(CH2Cl)3:[2]

3 Ph2PNa + CH3C(CH2Cl)3 → CH3C[CH2PPh2]3 + 3 NaCl

It forms complexes with many transition metals, usually as a tripodal ligand.[3] Such complexes are used to analyze mechanistic aspects of homogeneous catalysts.[4] For example, rhodium forms complexes with CH3C[CH2PPh2]3 like [(triphos)RhCl(C2H4)], [(triphos)RhH(C2H4)], and [(triphos)Rh(C2H5)(C2H4)], provide model intermediates in the catalytic cycle for hydrogenation of alkenes.[5]

Triphos sometimes behaves as a bidentate ligand. Illustrative cases include fac-[Mn(CO)3Br(η2-triphos)] and [M(CO)4(η2-triphos)], where M is Cr, Mo, or W. Triphos serves as a tridentate-bridging ligand in an icosahedral Au13 cluster. The phosphine bridges three chlorogold(I) groups to form the tripod molecule of trichloro-1,1,1-(diphenylphosphinomethyl)ethanetrigold(I), CH3C[CH2PPh2AuCl]3.[6]

Bis(diphenylphosphinophenyl)phenylphosphine

Like bis(diphenylphosphinoethyl)phenylphosphine, bis(diphenylphosphinophenyl)phenylphosphine is a linear tridentate ligand, but it is more rigid and more air stable. It is prepared from o-lithiated triphenylphosphine:[7]

2 LiC6H4PPh2 + PhPCl2 → PhP[C6H4PPh2]2

References
  1. "Synthesis of Polytertiary Phosphines and ‘Mixed’ Phosphorus–Sulphur and ‘Mixed’ Phosphorus–Nitrogen Polydentate Ligands via Free-Radical Catalysis" Daniel L. DuBois, William H. Myers and Devon W. Meek J. Chem. Soc., Dalton Trans., 1975, 1011-1015.doi:10.1039/DT9750001011
  2. W. Hewertson & H. R. Watson (1962). "283. The preparation of di- and tri-tertiary phosphines". J. Chem. Soc.: 1490–1494. doi:10.1039/JR9620001490.
  3. Huttner, G.; Strittmatter, J.; Sandhoefner, S. (2004). "Phosphorus Tripodal Ligands". Comprehensive Coordination Chemistry II. 1. pp. 297–322. doi:10.1016/B0-08-043748-6/01082-3. ISBN 9780080437484.CS1 maint: uses authors parameter (link)
  4. Bianchini, Claudio; Marchi, Andrea; Marvelli, Lorenza; Peruzzini, Maurizio; Romerosa, Antonio; Rossi, Roberto (1996). "Multiple Re-C Bonds at the [{MeC(CH2PPh2)3}Re(CO)2]+ Auxiliary". Organometallics. 15: 3804. doi:10.1021/om9602264.
  5. Bianchini, Claudio; Meli, Andrea; Peruzzini, Maurizio; Vizza, Francesco (1990). "Tripodal Polyphosphine Ligands in Homogeneous Catalysis. 1. Hydrogenation and Hydroformylation of Alkynes and Alkenes Assisted by Organorhodium Complexes with MeC(CH2PPh2)3". Organometallics. 9: 226–240. doi:10.1021/om00115a035.
  6. Cooper, Mervyn K.; Henrick, Kim; McPartlin, Mary & Latten, Jozef L. (1982). "The synthesis and X-ray structure of trichloro-1,1,1-(diphenylphosphinomethyl)ethanetrigold(I)". Inorganica Chimica Acta. 65 (2): L185. doi:10.1016/S0020-1693(00)93540-0.
  7. Hartley, J. G., Venanzi, L. M., Goodall, D. C., "The preparation and complex-forming properties of one tritertiary and one tetratertiary phosphine", J. Chem. Soc. 1963, 3930. doi:10.1039/JR9630003930
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