71763-25-2

Basic information

• Product Name: {(η5-C5H5)Re(NO)(PPh3)(CH2PPh3)}(+)PF6(-)
• Synonyms: {(η5-C5H5)Re(NO)(PPh3)(CH2PPh3)}(+)PF6(-)
• CAS NO: 71763-25-2
• Molecular Weight: 964.881
• Mol File: 71763-25-2.mol
• Article Data: 4

Chemical Properties

• CAS DataBase Reference: {(η5-C5H5)Re(NO)(PPh3)(CH2PPh3)}(+)PF6(-)(CAS DataBase Reference)
• NIST Chemistry Reference: {(η5-C5H5)Re(NO)(PPh3)(CH2PPh3)}(+)PF6(-)(71763-25-2)
• EPA Substance Registry System: {(η5-C5H5)Re(NO)(PPh3)(CH2PPh3)}(+)PF6(-)(71763-25-2)

Safety Data

• Hazardous Substances Data: 71763-25-2(Hazardous Substances Data)

Upstream product

• 437-17-2 tritylium hexafluorophosphate 
• 3878-45-3 triphenylphosphine sulfide 
• 603-35-0 triphenylphosphine 
• 80136-89-6 ((C₅H₅)Re(NO)(P(C₆H₅)3)CH₂)2SCH₃⁽¹⁺⁾*PF₆^(1-)=[((C₅H₅)Re(NO)(P(C₆H₅)3)CH₂)2SCH₃]PF₆ 
• 84369-18-6 {(η5-C5H5)Re(NO)(PPh3)(η2-H2C=S)}(+)PF6(-) 
• 71763-23-0 [(η(5)-cyclopentadienyl)Re(NO)(P(C6H5)3)(methylidene)]PF6 
• 80136-84-1 (C₅H₅)Re(NO)(P(C₆H₅)3)(CH₂S(CH₃)2)⁽¹⁺⁾*PF₆^(1-)=[(C₅H₅)Re(NO)(P(C₆H₅)3)(CH₂S(CH₃)2)]PF₆ 

Relevant articles and documents

Synthesis, structure, and reactivity of the thioformaldehyde complex [(η5-C5H5)Re(NO)(PPh 3)(η2-H2C=S)]+PF 6-

Reaction of [(η5-C5H5)Re(NO)(PPh3)(=CH 2)]+PF6- (2) and S=PPh3 gives a 1:1 mixture of thioformaldehyde complex [(η5-C5H5)Re(NO)(PPh 3)(η2-H2C=S)]+PF 6- (1) and ylide complex [(η5-C5H5)Re-(NO)(PPh3)(CH 2PPh3)]+PF6- (3). However, reaction of 2 and cyclohexene sulfide gives 1 (85-95% after recrystallization). An X-ray structure of 1 (crystal data: monoclinic, P21/c; a = 9.688 (2) A?, b = 18.536 (4) A?, c = 14.895 (s) A?; β= 103.53 (2)°; Z = 4) shows that the η2-H2C=S ligand adopts a conformation that has significant overlap of its π* orbital with the rhenium fragment HOMO and its sulfur terminus syn to the PPh3. Extended Hu?ckel MO calculations on the model compound [(η5-C5H5)Re(NO)-(PH 3)(η2-H2C=S)]+ predict a similar conformational energy minimum. Complex 1 is stable in CD3CN (41 h, 51°C) but rapidly reacts with PPh3 (2 equiv) to give 3 (95%) and S=PPh3 (88%). Reaction of 1 and NaBH3CN gives thiomethyl complex (η5-C5H5)Re(NO)(PPh3)(SCH 3) (5, 85% after recrystallization). The reactivity of 1 is compared to that of formaldehyde complex [(η5-C5H5)Re(NO)(PPh 3)(η2-H2C=O)]+ PF6-, and the mechanisms of the above reactions are discussed.

MECHANISM OF COUPLING OF equals CH2 TO H2C equals CH2 AT A HOMOGENEOUS ( eta -C5H5)Re(NO)(PPH3) + CENTER. REMARKABLE ENANTIOMER SELF-RECOGNITION.

The methylidene complex couples to the ethylene complex at 273-308 K in CH//2Cl//2. The rate of coupling is second order in 1 and not affected by the presence of 5-10 equiv of RCN. Data collected from 273 to 308 K give numerical results. Crossover experiments show that no PPh//3 dissociation or intermolecular methylidene scrambling occurs prior to the rate-determining coupling step, and that the RR and SS transition states are greatly preferred over the RS transition state (enantiomer self-recognition). 84 refs.