Triphos

Triphos

Names
IUPAC name Bis(diphenylphosphinoethyl)phenylphosphine
Other names Triphos
Identifiers
CAS Number	23582-02-7
3D model (Jmol)	Interactive image
ChemSpider	81424
PubChem	90192
InChI 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 Key: AXVOAMVQOCBPQT-UHFFFAOYSA-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
SMILES 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
Chemical formula	C34H29P3
Molar mass	534.55 g/mol
Appearance	white crystals
Melting point	129 to 130 °C (264 to 266 °F; 402 to 403 K)
Solubility in water	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
CAS Number	22031-12-5
3D model (Jmol)	Interactive image
ChemSpider	375165
PubChem	423856
InChI 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
SMILES 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
Chemical formula	C41H39P3
Molar mass	624.67 g/mol
Appearance	white crystals
Melting point	99 to 102 °C (210 to 216 °F; 372 to 375 K)
Solubility in water	Insoluble
Hazards
Safety data sheet	Triphos MSDS
S-phrases	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

Triphos is the name for certain organophorus 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 is 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. It usually functions as a tripodal ligand that occupies three adjacent coordination sites.^[3] Triphos complexes often exhibit high thermal stability. 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-chelating ligand. Illustrative cases include fac-[Mn(CO)₃Br(η²-triphos)] and [M(CO)₄(η²-triphos)],where M is Cr, Mo, or W.^[3] Triphos serves as a tridentate-bridging ligand in an icosohedral 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. Fernández, Eduardo J.; Gimeno, M. Concepción; Laguna, Antonio; Laguna, Mariano; López-de-Luzuriaga, José M. & Olmos, Elena (1996). "Different Coordination modes of 1,1,1-tris(diphenylphosphinomethyl) ethane Ligand in Gold(I) and Gold(III) Complexes". Journal of Organometallic Chemistry. 514: 169. doi:10.1016/0022-328X(95)06025-R.
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. 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