Tris(dimethylamino)phosphine

Tris(dimethylamino)phosphine
Names
	Preferred IUPAC name N,N,N′,N′,N′′,N′′-Hexamethylphosphanetriamine
	Other names Hexamethylphosphorous triamide; HMPT;
Identifiers
CAS Number	1608-26-0;
3D model (JSmol)	Interactive image;
ChemSpider	14616;
ECHA InfoCard	100.015.032
EC Number	216-534-4;
Gmelin Reference	906778
PubChem CID	15355;
RTECS number	TH3390000;
UNII	6072HG2UW4;
CompTox Dashboard (EPA)	DTXSID6061816;
	InChI InChI=1S/C6H18N3P/c1-7(2)10(8(3)4)9(5)6/h1-6H3 Key: XVDBWWRIXBMVJV-UHFFFAOYSA-N;
	SMILES CN(C)P(N(C)C)N(C)C;
Properties
Chemical formula	C6H18N3P
Molar mass	163.205 g·mol−1
Appearance	colorless liquid
Density	0.898 g/cm3
Boiling point	49 °C (120 °F; 322 K) 11 torr
Hazards
	GHS labelling:
Pictograms
Signal word	Warning
Hazard statements	H226
Precautionary statements	P210, P233, P240, P241, P242, P243, P280, P303+P361+P353, P370+P378, P403+P235, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Tris(dimethylamino)phosphine is an organophosphorus compound with the formula P(NMe₂)₃ (Me = methyl). It is a colorless oil at room temperature, and is one of the most common aminophosphines. Its structure has been determined by X-ray crystallography.^[2]

Tris(dimethylamino)phosphine acts as a base. It reacts with oxygen to give hexamethylphosphoramide, O=P(NMe₂)₃, and with sulfur to give the corresponding compound hexamethylthiophosphoramide, S=P(NMe₂)₃. It can also act as a ligand, forming complexes with a variety of metal centers.^[3] Its steric and electronic properties are similar to those of triisopropylphosphine.^[4]

Because of its affinity for sulfur, tris(dimethylamino)phosphine is also effective as a desulfurization agent, e.g., in the conversion of dibenzyl disulfide into dibenzyl sulfide:^[5]

PhCH₂SSCH₂Ph + P(NMe₂)₃ → S=P(NMe₂)₃ + PhCH₂SCH₂Ph (Ph = phenyl)

^ ^a ^b This name is also used to refer to hexamethylphosphoramide
^ Mitzel, Norbert W.; Smart, Bruce A.; Dreihäupl, Karl-Heinz; Rankin, David W. H.; Schmidbaur, Hubert (1996). "Low Symmetry in P(NR₂)₃ Skeletons and Related Fragments: An Inherent Phenomenon". Journal of the American Chemical Society. 118 (50): 12673–12682. doi:10.1021/ja9621861.
^ King, R. B. (1963). "Complexes of Trivalent Phosphorus Derivatives. II. Metal Carbonyl Complexes of Tris(dimethylamino)-phosphine". Inorganic Chemistry. 2 (5): 936–944. doi:10.1021/ic50009a014.
^ Tolman, C. A. (1977). "Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis". Chem. Rev. 77 (3): 313–348. doi:10.1021/cr60307a002.
^ Harpp, David N.; Smith, Roger A. (1978). "Sulfide Synthesis: Benzyl Sulfide". Org. Synth. 58: 138. doi:10.15227/orgsyn.058.0138.

[HMPT-1] This name is also used to refer to hexamethylphosphoramide

[2] Mitzel, Norbert W.; Smart, Bruce A.; Dreihäupl, Karl-Heinz; Rankin, David W. H.; Schmidbaur, Hubert (1996). "Low Symmetry in P(NR₂)₃ Skeletons and Related Fragments: An Inherent Phenomenon". Journal of the American Chemical Society. 118 (50): 12673–12682. doi:10.1021/ja9621861.

[3] King, R. B. (1963). "Complexes of Trivalent Phosphorus Derivatives. II. Metal Carbonyl Complexes of Tris(dimethylamino)-phosphine". Inorganic Chemistry. 2 (5): 936–944. doi:10.1021/ic50009a014.

[Tolman-4] Tolman, C. A. (1977). "Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis". Chem. Rev. 77 (3): 313–348. doi:10.1021/cr60307a002.

[5] Harpp, David N.; Smith, Roger A. (1978). "Sulfide Synthesis: Benzyl Sulfide". Org. Synth. 58: 138. doi:10.15227/orgsyn.058.0138.

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