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 · Mon Dec 31 23:00:00 EST 1990 · 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), 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
ALKYNES
ALLOYS
AMBIENT TEMPERATURE
CARBENES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
HYDROCARBONS
INFRARED SPECTRA
MASS SPECTRA
MASS SPECTROSCOPY
MERCURY ALLOYS
NMR SPECTRA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RADICALS
REDUCING AGENTS
REDUCTION
RUTHENIUM COMPLEXES
SPECTRA
SPECTROSCOPY
SYNTHESIS
THIOLS
TRANSITION ELEMENT COMPLEXES