Metathetical reactions of Re(VII) alkylidene-alkylidyne complexes of the type Re(CR[prime])(CHR[prime])[OCMe(CF[sub 3])[sub 2]][sub 2] (R[prime] = CMe[sub 3] or CMe[sub 2]Ph) with terminal and internal olefins

Journal Article · Wed Jan 13 00:00:00 EST 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00054a018· OSTI ID:6483219

Toreki, R; Vaughan, G A; Schrock, R R; Davis, W M ^[1]

---

1. Massachusetts Inst. of Technology, Cambridge (United States)

1-Decene and methyl 9-decenoate react with syn- and anti-Re(C-t-Bu)(CH-t-Bu)(OR[sub F6]) to give syn- and anti-Re(C-t-Bu)[CH(CH[sub 2])[sub 7]Me](OR[sub F6])[sub 2] and syn- and anti-Re(C-t-Bu)[CH(CH[sub 2])[sub 7]CO[sub 2]Me](OR[sub F6])[sub 2], respectively (OR[sub F6] = OCMe(CF[sub 3])[sub 2]). The new alkylidene complexes are unstable in the presence of excess terminal olefin and decompose upon attempted isolation. However, vinylferrocene reacts relatively smoothly and reversibly with syn-Re(C-t-Bu)(CH-t-Bu)(OR[sub F6])[sub 2] in a noncoordinating solvent to yield tert-butylethylene and primarily anti-Re(C-t-Bu)(CHFc)(OR[sub F6])[sub 2] (Fe = ferrocenyl). anti-Re(C-t-Bu)(CHFc)(OR[sub F6])[sub 2]. In the presence of THF or dimethoxyethane, complexes of the type syn- or anti-Re(C-t-Bu)(CHR)(OR[sub F6])S[sub 2] (R = Me, Et, Ph; S = THF or 0.5DME) could be prepared in high yield from Re(C-t-Bu)(CH-t-Bu)(OR[sub F6])[sub 2] and CH[sub 2][double bond]CHR. Heteroatom-substituted (O, S, or N) terminal olefins react more rapidly than ordinary olefins with Re(C-t-Bu)(CH-t-Bu)(OR[sub F6])[sub 2] in the presence of THF to yield complexes of the type syn- or anti-Re(C-t-Bu)(CHX)(OR[sub F6])[sub 2](THF)[sub 2] (X = OR, SR, NR[sub 2], or p-dimethylaminophenyl). 2-Pentene or methyl oleate is metathesized in the presence of Re(C-t-Bu)(CH-t-Bu)(OR[sub F6])[sub 2], and intermediate alkylidene complexes can be observed in each case. Addition of 3-hexene to Re(C-t-Bu)(CH-t-Bu)(OR[sub F6])[sub 2] followed by TMEDA yields Re(C-t-Bu)(CHEt)(OR[sub F6])[sub 2](TMEDA). Internal olefins are metathesized only very slowly by Re(C-t-Bu)(CH-t-Bu)(OR[sub F6])[sub 2] in the presence of several equivalents of THF or DME or especially in neat THF or DME. 58 refs., 4 figs., 4 tabs.

• OSTI ID: 6483219
• Journal Information: Journal of the American Chemical Society; (United States), Vol. 115:1; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKENES
CHEMICAL REACTIONS
ORGANOMETALLIC COMPOUNDS
RHENIUM COMPLEXES
CHEMICAL REACTION YIELD
HOMOGENEOUS CATALYSIS
LIGANDS
SOLVENTS
CATALYSIS
COMPLEXES
HYDROCARBONS
ORGANIC COMPOUNDS
TRANSITION ELEMENT COMPLEXES
YIELDS
400201* - Chemical & Physicochemical Properties