Trimethylolpropane phosphite

Trimethylolpropane phosphite
Names
	Preferred IUPAC name 4-Ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane
	Other names EtCage; Ethyl bicyclic phosphite; Trishydroxymethylpropane bicyclic phosphite
Identifiers
CAS Number	824-11-3 ;
3D model (JSmol)	Interactive image;
ChemSpider	12655 ;
ECHA InfoCard	100.011.385
EC Number	212-523-3;
PubChem CID	13210;
UNII	1ND7080ZYD ;
CompTox Dashboard (EPA)	DTXSID10871809 ;
	InChI InChI=1S/C6H11O3P/c1-2-6-3-7-10(8-4-6)9-5-6/h2-5H2,1H3 Key: QRUSNTDXJQBKBI-UHFFFAOYSA-N ; InChI=1/C6H11O3P/c1-2-6-3-7-10(8-4-6)9-5-6/h2-5H2,1H3 Key: QRUSNTDXJQBKBI-UHFFFAOYAD;
	SMILES O1P2OCC(CC)(C1)CO2;
Properties
Chemical formula	C6H11O3P
Molar mass	162.125 g·mol−1
Appearance	white waxy solid
Melting point	56 °C (133 °F; 329 K)
Solubility in water	organic solvents
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Trimethylolpropane phosphite, C₂H₅C(CH₂O)₃P, is a phosphite ester used as a ligand in organometallic chemistry. Trimethylolpropane phosphite is sometimes abbreviated to EtCage. It is a white solid that is soluble in organic solvents. It is also highly toxic.^[1]

Preparation and reactions

It is prepared by reaction of trimethylolpropane with phosphorus trichloride or by transesterification with trimethylphosphite:^[2]

P(OMe)₃ + EtC(CH₂OH)₃ → 3 MeOH + EtC(CH₂O)₃P

The first member of this series was derived from trimethylolethane,^[3] but these derivatives are often poorly soluble. For this reason, the ethyl derivative has received more attention.^[4]

Reactions

The compound forms an isolable ozonide, which degrades above 0 °C to release singlet O₂.^[1]

Coordination chemistry

Several EtCage complexes are known, since the ligand is highly basic (for a phosphite) and has a small ligand cone angle (101°). Illustrative complexes include [(EtCage)₂Mo(CO)₄], [Ir₄(CO)₁₁(EtCage)] and (CpMe₅)RuCl(EtCage)₂, shown below.

Safety

Trimethylolpropane phosphite is very toxic and is a convulsant. LD50 is 1.1 mg per kg bodyweight (mice, i.p.).^[5]^[6]

References

^ ^a ^b Ende, Christopher; Parker, Kathlyn (2014). "4-Ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane". e-EROS Encyclopedia of Reagents for Organic Synthesis. pp. 1–3. doi:10.1002/047084289X.rn01781. ISBN 9780470842898.
^ Verkade, J. G. "Spectroscopic studies of metal-phosphorus bonding in coordination complexes" Coordination Chemistry Reviews 1972, vol. 9, 1-106. doi:10.1016/S0010-8545(00)80224-6
^ Verkade, J. G.; Reynolds, L. T. "The synthesis of a novel ester of phosphorus and of arsenic" Journal of Organic Chemistry (1960), 25, 663-5. doi:10.1021/jo01074a622
^ Huttemann, T. J., Jr.; Foxman, B. M.; Sperati, C. R.; Verkade, J. G. "Transition metal complexes of a constrained phosphite ester. IV. Compounds of cobalt(I), cobalt(III), nickel(II), and nickel(0)" Inorganic Chemistry (1965), 4(7), 950-3. doi:10.1021/ic50029a005
^ Ralf Stöhr et al. Chemische Kampfstoffe und Schutz vor chemischen Kampfstoffen 2. Aufl. Militärverlag der DDR, 1985 (german)
^ Milbrath, Dean S.; Engel, Judith L.; Verkade, John G.; Casida, John E. (1979). "Structure-toxicity relationships of 1-substituted-4-alkyl-2,6,7-trioxabicyclo[2.2.2.]octanes". Toxicology and Applied Pharmacology. 47 (2): 287–93. Bibcode:1979ToxAP..47..287M. doi:10.1016/0041-008X(79)90323-5. PMID 452023.

[eros-1] Ende, Christopher; Parker, Kathlyn (2014). "4-Ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane". e-EROS Encyclopedia of Reagents for Organic Synthesis. pp. 1–3. doi:10.1002/047084289X.rn01781. ISBN 9780470842898.

[2] Verkade, J. G. "Spectroscopic studies of metal-phosphorus bonding in coordination complexes" Coordination Chemistry Reviews 1972, vol. 9, 1-106. doi:10.1016/S0010-8545(00)80224-6

[3] Verkade, J. G.; Reynolds, L. T. "The synthesis of a novel ester of phosphorus and of arsenic" Journal of Organic Chemistry (1960), 25, 663-5. doi:10.1021/jo01074a622

[4] Huttemann, T. J., Jr.; Foxman, B. M.; Sperati, C. R.; Verkade, J. G. "Transition metal complexes of a constrained phosphite ester. IV. Compounds of cobalt(I), cobalt(III), nickel(II), and nickel(0)" Inorganic Chemistry (1965), 4(7), 950-3. doi:10.1021/ic50029a005

[5] Ralf Stöhr et al. Chemische Kampfstoffe und Schutz vor chemischen Kampfstoffen 2. Aufl. Militärverlag der DDR, 1985 (german)

[6] Milbrath, Dean S.; Engel, Judith L.; Verkade, John G.; Casida, John E. (1979). "Structure-toxicity relationships of 1-substituted-4-alkyl-2,6,7-trioxabicyclo[2.2.2.]octanes". Toxicology and Applied Pharmacology. 47 (2): 287–93. Bibcode:1979ToxAP..47..287M. doi:10.1016/0041-008X(79)90323-5. PMID 452023.

[1]

[2]

[3]

[4]

[5]

[6]