74363-95-4

Upstream product

• 30540-36-4 3,4-dimethyl-1-phenylphosphole 
• 36477-75-5 tungsten pentacarbonyl tetrahydrofuran 

Downstream Products

• 113892-44-7 cis-(butylethoxycarbene)(1-phenyl-3,4-dimethylphosphole)tetracarbonyltungsten 
• 113892-45-8 cis-(phenylethoxycarbene)(1-phenyl-3,4-dimethylphosphole)tetracarbonyltungsten 
• 83576-97-0 W(CO)5P(C₆H₅)C₆H₄(CH₃)2(CON(C₆H₅)CO) 
• 82265-68-7 (1,2,3-triphenylphosphirene)pentacarbonyltungsten 
• 82265-64-3 syn-[5,6-dimethyl-2,3-bis(methoxycarbonyl)-7-phenyl-7-phosphanorbornadiene]pentacarbonyltungsten 
• 97704-77-3 (3,4-diphenyl-2-oxo-1,2-dihydrophosphete(P-W))-pentacarbonyltungsten 
• 97704-78-4 (3,4-diethyl-2-oxo-1,2-dihydrophosphete(P-W))pentacarbonyltungsten 

Relevant academic research and scientific papers

Phosphinidene reactivity toward unsaturated phosphorus heterocycles

The transient electrophilic phosphinidene complex PhPW(CO)5 reacts in the presence of CuCl at room temperature with phospholene 2 and phospholes 4a-c to give the corresponding W(CO)5 complexed products 3 and 5a-c. The intermediate phosphoranylidene phosphine complexes, formed, from the addition of PhPW(CO)5 to the phosphorus atom of the substrates, are characterized by NMR spectroscopy and by a single crystal X-ray structure determination for the one generated from phospholene 2. This intermediate 8 is a CuCl-complexed dimer, which speculatively results from dissociating the phosphole-CuCl tetramer on insertion of PhPW(CO)5 into the P-Cu bonds. Reacting PhPW(CO)5 with phospholene 2 at 110°C in the absence of CuCl gives besides the W(CO)5-complexed phospholene 3 also a bisphospholene-W(CO)4 complex 13. The formation of 13 is attributed to a ligand exchange reaction in the intermediate phosphinidene-phospholene adduct.

SYNTHESIS AND STEREOCHEMISTRY OF PENTACARBONYL(PHOSPHOLE)METAL(0)- AND TETRACARBONYLBIS(PHOSPHOLE)METAL(0) COMPLEXES OF 6B ELEMENTS

Pentacarbonylphospholemetal(0) and cis-tetracarbonylbis(phosphole)metal(0) complexes were synthesized from the thermal reaction of M(CO)5(THF) and M(CO)4(COD) (M: Cr, Mo, W) with corresponding phosphole (1-phenyl-3,4-dimethylphosphole, 1-phenyl-3-methylphosphole, and 1-phenylphosphole).These complexes were isolated as orange crystals by column chromatography on silicagel at 253 K and crystallization from n-hexane at 223 K and characterized by means of IR and NMR (1H, 13C, and 31P).Spectroscopic data shows that the phosphole is coordinated to the transition metal through its phosphorus atom rather than through the conjugated diene unit in the both types of complexes.The tetracarbonylbis(phosphole)metal(0) complexes were found to have cis-arrangement of two phosphole ligands.Comparing 13C-NMR chemical shifts of the complexes with the free ligands, one can deduce that the involvement of the phosphorus atom in the ring ?-electron delocalization is drastically reduced upon coordination.This is attributed to the stronger ?-donation but weaker ?-accepting ability of the phosphorus atom in the phosphole ligands compared to the carbonyl groups. Key words: Phosphole; chromium; molybdenum; tungsten; carbonyl