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 04:00:00 EST 1991 · Organometallics; (United States)

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

Miller, D C; Angelici, R J ^[1]

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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), Journal Name: Organometallics; (United States) Vol. 10:1; ISSN 0276-7333; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

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