Vinylidene, acetylide, and carbene complexes from reactions of 2,5-dithiahex-3-yne (MeSC triple bond CSMe) with Cp(PMe sub 3 ) sub 2 Ru sup +

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

DOI:https://doi.org/10.1021/om00047a033· OSTI ID:5926336

Miller, D C; Angelici, R J ^[1]

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1. Ames Lab., IA (United States)

The alkyne MeSC{triple bond}CSMe initially displaces Cl{sup {minus}} in Cp(PMe{sub 3}){sub 2}RuCl at room temperature in MeOH to form the sulfur-bound alkyne complex {l brace}Cp(PMe{sub 3}){sub 2}Ru(S(Me)C{triple bond}CSMe){r brace}PF{sub 6} (1). When it is warmed 1 rearranges to the vinylidene complex (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}C(SMe){sub 2})PF{sub 6} (2). Complex 2 is reduced by Na(HBEt{sub 3}) or Na/Hg to give the thioacetylide Cp(PMe{sub 3}){sub 2}Ru-C{triple bond}CSMe (5) and MeSSMe. The vinylidene complexes (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}C(R)(SMe)){sup +} (6, R = H; 7, R = Me) are formed by electrophilic addition to the {beta}-carbon of the thioacetylide 5. Addition of CuCl to 5 forms Cp(PMe{sub 3}){sub 2}Ru(C{triple bond}CSMe)(CuCl) (8), in which the copper is {pi}-bound through the C{triple bond}C group. Reaction of 6 with methanol and ethanol yields the alkoxycarbene complexes (Cp(PMe{sub 3}){sub 2}Ru{double bond}C(OR)(CH{sub 2}SMe))BF{sub 4} (11a, R = Me; 11b, R = Et). Deprotonation of 11a with NaOMe yields the vinyl complex Cp(PMe{sub 3}){sub 2}Ru(C(OMe){double bond}C(H)SMe) (12). Addition of (Me{sub 3}O)BF{sub 4} to complexes 6 and 7 yields the first examples of sulfoniovinylidene dicationic complexes (Cp(PMe{sub 3}){sub 2}Ru{double bond}C{double bond}C(R)(SMe{sub 2}))(BF{sub 4}){sub 2} (9, R = H; 10, R = Me). Complexes 7 and 10 undergo one- and two-electron reductions, respectively, to give the acetylide Cp(PMe{sub 3}){sub 2}Ru-C{triple bond}CMe (14) and MeSSMe (for 7) or SMe{sub 2} (for 10). Complexes 6 and 9 are readily deprotonated to give 5 and the sulfonioacetylide (Cp(PMe{sub 3}){sub 2}Ru-C{triple bond}CSMe{sub 2})BF{sub 4} (13), respectively. Mechanisms of the reactions and structural features of the vinylidenes are discussed.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5926336
• 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
ALKYNES
REDUCTION
RUTHENIUM COMPLEXES
CHEMICAL PREPARATION
ALKENES
AMBIENT TEMPERATURE
CARBENES
INFRARED SPECTRA
MASS SPECTRA
MASS SPECTROSCOPY
MERCURY ALLOYS
NMR SPECTRA
ORGANIC SULFUR COMPOUNDS
REDUCING AGENTS
THIOLS
ALLOYS
CHEMICAL REACTIONS
COMPLEXES
HYDROCARBONS
ORGANIC COMPOUNDS
RADICALS
SPECTRA
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties