82281-49-0

Upstream product

• 88080-18-6 [1-phenyl-2-methyl-2-(1-methylvinyl)phosphirane]pentacarbonyltungsten 
• 14409-95-1 1-phenyl-3,4-dimethyl-2,5-dihydro-1H-phosphole 
• 852242-57-0 3-phenyl-3H-3-benzophosphenine pentacarbonyltungsten⁽⁰⁾ 
• 513-81-5 2,3-dimethyl-buta-1,3-diene 
• 333304-08-8 [(CH₃)2C₄H₄P(C₆H₅)P(C₆H₅)(W(CO)5)CuCl]2 
• 82265-64-3 syn-[5,6-dimethyl-2,3-bis(methoxycarbonyl)-7-phenyl-7-phosphanorbornadiene]pentacarbonyltungsten 

Relevant academic research and scientific papers

Phosphepines: Convenient access to phosphinidene complexes

Reaction of o-diethynylbenzene with transition metal-complexed primary phosphines gives in a single base-induced step stable phosphepine complexes as confirmed by X-ray data. At 75-80 °C these phosphepines undergo clean cheletropic elimination of naphthalene to give transient carbene-like phosphinidene complexes that can be trapped in high yield by alkenes, alkynes, and alcohols. Copyright

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.

The carbene-like behavior of terminal phosphinidene complexes toward olefins. A new access to the phosphirane ring

In the presence of copper(I) chloride, (7-R-7-phosphanorbornadiene)P-M(CO)5 complexes (M = Cr, W) decompose around 55°C to give the corresponding terminal phosphinidene complexes RP=M(CO)5. These transient phosphinidene complexes react in situ with olefins to give phosphirane complexes. The stereochemistry of the starting olefin is retained in the phosphirane ring, thus suggesting a concerted process. The reaction with 1,3-dienes yields 2-vinylphosphirane complexes that rearrange around 100°C to the corresponding phospholenes. On the contrary, the reaction with α,β-unsaturated ketones gives directly the 1,2-oxaphospholene complexes, but the formation of an intermediate 2-acylphosphirane cannot be excluded. With methyl methacrylate, the 2-(methoxycarbonyl)phosphirane is formed and is apparently stable. With ethyl vinyl ether, the 2-ethoxyphosphirane transiently obtained is so reactive that neutral water cleaves the P-C(OEt) bond of the ring to give a secondary α-phosphinoacetaldehyde that is stabilized as its P-W(CO)5 complex. An excess of vinyl ether also reacts with the 2-ethoxyphosphirane to give a 2,4-diethoxyphospholane. In all its reactions, PhP=W(CO)5 apparently behaves as a singlet electrophilic carbene.