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Triphos

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Triphos
Names
IUPAC name
Bis(diphenylphosphinoethyl)phenylphosphine
Other names
Triphos
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/C34H33P3/c1-6-16-30(17-7-1)35(26-28-36(31-18-8-2-9-19-31)32-20-10-3-11-21-32)27-29-37(33-22-12-4-13-23-33)34-24-14-5-15-25-34/h1-25H,26-29H2 ☒N
    Key: AXVOAMVQOCBPQT-UHFFFAOYSA-N ☒N
  • InChI=1/C34H33P3/c1-6-16-30(17-7-1)35(26-28-36(31-18-8-2-9-19-31)32-20-10-3-11-21-32)27-29-37(33-22-12-4-13-23-33)34-24-14-5-15-25-34/h1-25H,26-29H2
    Key: AXVOAMVQOCBPQT-UHFFFAOYAR
  • C1=CC=C(C=C1)P(CCP(C2=CC=CC=C2)C3=CC=CC=C3)CCP(C4=CC=CC=C4)C5=CC=CC=C5
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).
☒N verify (what is checkY☒N ?)
Triphos
Names
IUPAC name
1,1,1-Tris(diphenylphosphinomethyl)ethane
Other names
Triphos,
tdppme,
tdme
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/C41H39P3/c1-41(32-42(35-20-8-2-9-21-35)36-22-10-3-11-23-36,33-43(37-24-12-4-13-25-37)38-26-14-5-15-27-38)34-44(39-28-16-6-17-29-39)40-30-18-7-19-31-40/h2-31H,32-34H2,1H3
    Key: BARUNXKDFNLHEV-UHFFFAOYSA-N
  • InChI=1/C41H39P3/c1-41(32-42(35-20-8-2-9-21-35)36-22-10-3-11-23-36,33-43(37-24-12-4-13-25-37)38-26-14-5-15-27-38)34-44(39-28-16-6-17-29-39)40-30-18-7-19-31-40/h2-31H,32-34H2,1H3
    Key: BARUNXKDFNLHEV-UHFFFAOYAL
  • CC(CP(C1=CC=CC=C1)C2=CC=CC=C2)(CP(C3=CC=CC=C3)C4=CC=CC=C4)CP(C5=CC=CC=C5)C6=CC=CC=C6
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 (SDS) Triphos MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

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

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. ^ "Phosphorus Tripodal Ligands". Comprehensive Coordination Chemistry II. Vol. 1. 2004. pp. 297–322. doi:10.1016/B0-08-043748-6/01082-3. ISBN 9780080437484. {{cite encyclopedia}}: Unknown parameter |authors= ignored (help)
  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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