1418581-66-4

Upstream product

• 103055-90-9 {2,3-diphenyl-1-chlorophosphirene}pentacarbonyltungsten 
• 2923-28-6 silver trifluoromethanesulfonate 
• 1418581-52-8 [W(CO)₅{P(N-i-Pr₂)C(Ph)C(Ph)}] 
• 14040-11-0 tungsten hexacarbonyl 
• 501-65-5 diphenyl acetylene 

Downstream Products

• 101377-06-4 (1-allyl-2,3-diphenylphosphirene)pentacarbonyltungsten 
• 345197-84-4 [W(CO)₅{P(C₂Ph)C(Ph)C(Ph)}] 
• 1418581-63-1 [W(CO)₅{P(C₁₀H₉Fe)C(Ph)C(Ph)}] 
• 1531632-87-7 P{2-C₆H₃(2-N(CH₃)₂)(5-CH₃)}C(Ph)C(Ph) 
• 1531632-74-2 [W(CO)₅{P(p-C₆H₄N(CH₂CH₃)₂)C(Ph)C(Ph)}] 
• 1531632-75-3 [W(CO)₅{P{C₆H₃(2-N(CH₃)₂)(5-CH₃)}C(Ph)C(Ph)}] 
• 1531632-89-9 C₂₆H₁₇O₆PW 
• 1531632-77-5 [W(CO)₅{P(p-C₆H₄OCH₃)C(Ph)C(Ph)}] 
• 1531632-78-6 [W(CO)₅{P(2-C₄H₃S)C(Ph)C(Ph)}] 
• 1531632-79-7 [W(CO)₅{P(2-C₄H₃O)C(Ph)C(Ph)}] 
• 1531632-80-0 [W(CO)₅{P{3-C₄H(2,5-CH₃)₂O}C(Ph)C(Ph)}] 
• 1531632-81-1 [W(CO)₅{P(2-C₄H₃NH)C(Ph)C(Ph)}] 
• 1531632-82-2 [W(CO)₅{P(3-C₈H₅NH)C(Ph)C(Ph)}] 
• 1531632-83-3 [{W(CO)₅}2-μ-{C₈H₅N-1,3-{PC(Ph)C(Ph)}₂}] 

Relevant academic research and scientific papers

Electrophilic aromatic substitution reactions of a tungsten-coordinated phosphirenyl triflate

The phosphirenyl cation complex [W(CO)5{PC(Ph)C(Ph)}] + (2) is formed by chloride abstraction from the chlorophosphirene complex [W(CO)5{P(Cl)C(Ph)C(Ph)}] (1) with excess AlCl3. The phosphirenyl triflate complex [W(CO)5{P(OSO2CF 3)C(Ph)C(Ph)}] (3) is formed by reaction of the chlorophosphirene complex with AgOSO2CF3 and is in equilibrium with and typically reacts in the same fashion as the phosphirenyl cation. Reaction of 3 with diethylaniline or anisole leads to electrophilic aromatic substitution preferentially at the para position. Reaction with N,N-dimethyl-p-toluidine, in which the para position is blocked, leads to exclusive ortho substitution. The resulting 1,2-substituted arene can adopt a P,N bidentate coordination mode if a CO is removed from tungsten via photolysis. Compound 3 reacts with aromatic heterocycles thiophene, furan, and pyrrole, leading exclusively to substitution in the 2 position, with no evidence for P-S, P-O, or P-N bond formation. Reaction with indole led to substitution at the 3 position, also with no evidence for P-N bond formation. However, upon chromatographic purification, the substituted indole product decomposes into a disubstituted product, with W-coordinated phosphirenyl units at the 3 position and at N. Reaction with phenol and diphenyl amine led exclusively to P-O and P-N bond formation, with no evidence for aromatic substitution. Phosphine products can be removed via oxidation of W with I2, followed by displacement with bipyridine. A computational study shows that coordination to W(CO)5 greatly enhances electrophilicity at P in phosphenium ions, leading to the observed rapid electrophilic substitution reactions.

Facile phosphorus-carbon bond formation using a tungsten-coordinated phosphirenyl cation

Reaction of K2[W(CO)5] with Cl2PN-i- Pr2 in the presence of diphenylacetylene leads to the tungsten aminophosphirene complex [W(CO)5{P(N-i-Pr2)C(Ph)C(Ph)}] (1), which can be converted to th