Diastereoselective Addition of Mono‐ and Bis‐silylphosphines to Chiral Aldehydes.

Group 6 metal carbonyl complexes of a family of bulky phosphines: spectroscopic and structural studies of chromium(0)-, molybdenum(0)- and tungsten(0)-pentacarbonylsilylphosphines

“…The solid was re-dissolved in hexane and X-ray quality crystals of Cr(HP{TMS} 2 )(CO) 5 (7), were grown from slow evaporation of the solvent in an inert atmosphere glove box. Pure samples of Mo(HP{TMS} 2 )(CO) 5 (8) and W(HP {TMS} 2 )(CO) 5 (9) were also obtained; however, X-ray quality crystals were not formed. 31 Table 1 contains crystal data, collection parameters and refinement criteria for compounds 4-7.…”

“…pentane leaving a pale yellow/brown solid behind. The solid was re-dissolved in hexane and X-ray quality crystals of Cr(PhP{TMS} 2 )(CO) 5 (4), Mo(PhP{TMS} 2 ) (CO) 5 (5) and W(PhP{TMS} 2 ) (CO) 5 (6) were grown from slow evaporation of the solvent in an inert atmosphere glove box. (7), Mo (8), W (9) A solution of M(CO) 5 THF, M ¼ Cr, Mo and W was prepared by irradiating 1.1 mmol of the respective hexacarbonyl in 50 mL of THF using a high-pressure mercury lamp in 1-h increments with degassing for 3-4 h. The HP(TMS) 2 was generated by adding 0.041 mL (1.0 mmol) of dry, degassed CH 3 OH to 0.29 mL (1.0 mmol) of P(TMS) 3 in 2.5 mL of THF.…”

“…All the metal complexes (4-9) are readily prepared through direct reaction with the reactive M(CO) 5 THF intermediate as shown in Scheme 1. The extremely air-sensitive nature of the ligands requires that great care is taken to exclude oxygen and water from the reaction mixtures.…”

“…For example P(TMS) 3 has been recently reported for use in the synthesis of new wide-bite-angle diphosphines, indium-phosphide nanocrystals and chiral phosphabarrelene ligands [2][3][4]. The use of PhP(TMS) 2 is reported in the diasteroselective addition of silylphosphines to chiral aldehydes and preparation of heteronuclear pconjugated polymers [5,6]. Finally, HP(TMS) 2 has appeared in the literature for use in the synthesis of unique aluminum-phosphorus bonded compounds and functionalized alkylidenephosphines [7,8].…”