Formation of phosphino-substituted isocyanate by reaction of CO2 with group 2 complexes based on the (Me3Si)(i-Pr2P)NH ligand.
The group 2 complexes [(Me(3)Si)(i-Pr(2)P)N](2)M(THF)(x) (M = Mg, x = 1; M = Ca/Sr, x = 2) as well as an unusual dimagnesium complex {[(Me(3)Si)(i-Pr(2)P)N](3)Mg}Mg(n-C(4)H(9)) have been prepared and characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction. Each complex was shown to react with CO(2) under extremely mild conditions (15 min, 1 atm, room temperature) to give the isocyanate (i-Pr)(2)P-N═C═O. The independent syntheses of (i-Pr)(2)P-N═C═O and the carbodiimide dimer [(i-Pr)(2)PNCNP(i-Pr)(2)](2) are also reported.
Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
Diane A
DA
Dickie
Kevin B
KB
Gislason
Richard A
RA
Kemp
D002234:Carbodiimides / Q000737:chemistry; D002245:Carbon Dioxide; D018360:Crystallography, X-Ray; D017953:Isocyanates / Q000138:chemical synthesis / Q000737:chemistry*; D008024:Ligands; D008274:Magnesium / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry*
D002234:Carbodiimides; D017953:Isocyanates; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D002245:Carbon Dioxide; C044646:phosphine; D008274:Magnesium