Electrophilic and nucleophilic reactions of the vinylidene complex (Cp(PMe sub 3 ) sub 2 Ru double bond C double bond C(SMe) sub 2 )BF sub 4 and its derivatives

Journal Article · Tue Jan 01 00:00:00 EST 1991 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00047a034· OSTI ID:5714405

Miller, D C; Angelici, R J ^[1]

---

1. Ames Lab., IA (United States)

The cationic vinylidene complex (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}C(SMe){sub 2})BF{sub 4} (1) undergoes addition of electrophiles such as HBF{sub 4}{center dot}Et{sub 2}O, (MeSSMe{sub 2})SO{sub 3}CF{sub 3}, and (Me{sub 3}O)BF{sub 4} to give the complexes ((Ru) = Cp(PMe{sub 3}){sub 2}Ru) {l brace}Ru(S(Me)C{double bond}(H)SMe){r brace}(BF{sub 4}){sub 2} (2a), {l brace}Ru(S(Me)C{double bond}C(SMe)(H)){r brace}(BF{sub 4}){sub 2} (2b), {l brace}Ru(S(Me)C{double bond}C(H)SMe){sub 2}{r brace}(BF{sub 4}){sub 2} (3), and (Ru{double bond}C{double bond}C(SMe{sub 2})(SMe))(BF{sub 4}){sub 2} (4). An X-ray diffraction investigation shows that 2a crystallizes in space group C2/c with a = 31.558 (5) {angstrom}, b = 10.492 (2) {angstrom}, c = 16.484 (5) {angstrom}, {beta} = 100.89 (2){degree}, and Z = 8. The reaction of 4 with phosphines results in the cleavage of MeS{sup +} to form the sulfonio acetylide (Cp(PMe{sub 3}){sub 2}Ru-C{triple bond}CSMe{sub 2})BF{sub 4} (5) and (MeS-PPh{sub 2}R){sup +} (R = Me, Ph). Anionic nucleophiles such as NaSR (R = Et, Me) displace Me{sub 2}S from 4 to yield the vinylidene complexes (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}(SR)(SMe))BF{sub 4} (R = Et (7), R = Me (1)). Complex 4 also reacts with pyridines, 4-NC{sub 5}H{sub 4}R (R = H, Et, NMe{sub 2} (DMAP)), and SEt{sub 2} to displace Me{sub 2}S to yield the dicationic vinylidene complexes (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}C(4-NC{sub 5}H{sub 4}R)(SMe))(BF{sub 4}){sub 2} (R = H (8), Et (9), NMe{sub 2} (10)) and (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}C(SEt{sub 2})(SMe))(BF{sub 4}){sub 2} (11).

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5714405
• Journal Information: Organometallics; (United States), Vol. 10:1; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RUTHENIUM COMPLEXES
CHEMICAL REACTION KINETICS
BOND LENGTHS
CATIONS
CHEMICAL PREPARATION
CYCLOPENTADIENE
DITHIOLS
MASS SPECTRA
NMR SPECTRA
ORGANOMETALLIC COMPOUNDS
PHOSPHINES
REACTION INTERMEDIATES
SODIUM ALLOYS
THIOLS
X-RAY DIFFRACTION
ALKENES
ALLOYS
CHARGED PARTICLES
COHERENT SCATTERING
COMPLEXES
CYCLOALKENES
DIENES
DIFFRACTION
DIMENSIONS
HYDROCARBONS
IONS
KINETICS
LENGTH
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOSPHORUS COMPOUNDS
POLYENES
REACTION KINETICS
REAGENTS
SCATTERING
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties