Reactions of molybdenum and tungsten η2-C,C-vinyl complexes [Mη3-C(CF3)C(CF3)SR(CF3CCCF3)(η5-C5H5)] with alkynes leading to novel metallacycles

L. Carlton; Naz M. Agh-Atabay; Jack L. Davidson

Reactions of molybdenum and tungsten η²-C,C-vinyl complexes [Mη³-C(CF₃)C(CF₃)SR(CF₃CCCF₃)(η⁵-C₅H₅)] with alkynes leading to novel metallacycles

L. Carlton, Naz M. Agh-Atabay, Jack L. Davidson

School of Engineering & Physical Sciences

Research output: Contribution to journal › Article › peer-review

10 Citations (Scopus)

Abstract

The reactions of [M?³-C(CF₃)C(CF₃)SR(CF₃C=CCF₃)(?⁵-C₅H₅)](M = Mo, R = ⁱPr; M = W, R = Me, ⁱPr, ^tBu) with alkynes R'C=CR?, (R' = R? = Me, Et, Ph; R' = Ph, R? = Me) gives isomeric ?²-vinyl [M?³-C(CF₃)C(CF₃)C(R?)=C(R')(SR)(CF₃C=CCF₃)(?⁵-C₅H₅)] and/or ?⁴-butadienyl complexes [M?⁴-C(CF₃)C(CF₃)=C(R?)C(R')(SR)(CF₃C=CCF₃)(?⁵-C₅H₅)] (not all cases) apparently as a result of insertion of the incoming alkyne into the CS bond of the ?³-C(CF₃)C(CF₃)SR ligand. Thermolysis of [W?³-C(CF₃)C(CF₃)C(Me)=C(Ph)SⁱPr(CF₃C=CCF₃)(?⁵-C₅H₅)] in hexane at 55°C gives [WSⁱPr?⁵-C(CF₃)C(CF₃)C(CF₃)C(CF₃)C(Me)C(Ph)(?⁵-C₅H₅)]. In contrast thermolysis of [Mo?³-C(CF₃)C(CF₃)C(Me)=C(Me)SⁱPr(CF₃C=CCF₃)(?⁵-C₅H₅)] in hexane at 70°C gives [Mo?⁴-C(Me)C(Me)=C(CF₃)C(CF₃)(H)(CF₃C=CCF₃)(?⁵-C₅H₅)] via the intermediate [Mo?⁴-C(CF₃)C(CF₃)=C(Me)C(Me)SⁱPr(CF₃C=CCF₃)(?⁵-C₅H₅)]. Fluxional behaviour in complexes [M?³-C(CF₃)C(CF₃)C(R?)=C(R')(SR)(CF₃C=CCF₃)(?⁵-C₅H₅)] has been studied by variable temperature ¹⁹F NMR spectroscopy and two processes detected. The first involves rapid exchange between two isomeric forms and is ascribed to inversion at either the sulphur or the ß-carbon of the C(CF₃)C(CF₃)C(R?)=C(R')SR ligand. The second appears to involve restricted rotation of the CF₃ attached to the ß-carbon. © 1991.

Original language	English
Pages (from-to)	205-221
Number of pages	17
Journal	Journal of Organometallic Chemistry
Volume	413
Issue number	1-3
Publication status	Published - 7 Aug 1991

Cite this

@article{2d131fdf0646458690e37b617305c45f,

title = "Reactions of molybdenum and tungsten η2-C,C-vinyl complexes [Mη3-C(CF3)C(CF3)SR(CF3CCCF3)(η5-C5H5)] with alkynes leading to novel metallacycles",

abstract = "The reactions of [M?3-C(CF3)C(CF3)SR(CF3C=CCF3)(?5-C5H5)](M = Mo, R = iPr; M = W, R = Me, iPr, tBu) with alkynes R'C=CR?, (R' = R? = Me, Et, Ph; R' = Ph, R? = Me) gives isomeric ?2-vinyl [M?3-C(CF3)C(CF3)C(R?)=C(R')(SR)(CF3C=CCF3)(?5-C5H5)] and/or ?4-butadienyl complexes [M?4-C(CF3)C(CF3)=C(R?)C(R')(SR)(CF3C=CCF3)(?5-C5H5)] (not all cases) apparently as a result of insertion of the incoming alkyne into the CS bond of the ?3-C(CF3)C(CF3)SR ligand. Thermolysis of [W?3-C(CF3)C(CF3)C(Me)=C(Ph)SiPr(CF3C=CCF3)(?5-C5H5)] in hexane at 55°C gives [WSiPr?5-C(CF3)C(CF3)C(CF3)C(CF3)C(Me)C(Ph)(?5-C5H5)]. In contrast thermolysis of [Mo?3-C(CF3)C(CF3)C(Me)=C(Me)SiPr(CF3C=CCF3)(?5-C5H5)] in hexane at 70°C gives [Mo?4-C(Me)C(Me)=C(CF3)C(CF3)(H)(CF3C=CCF3)(?5-C5H5)] via the intermediate [Mo?4-C(CF3)C(CF3)=C(Me)C(Me)SiPr(CF3C=CCF3)(?5-C5H5)]. Fluxional behaviour in complexes [M?3-C(CF3)C(CF3)C(R?)=C(R')(SR)(CF3C=CCF3)(?5-C5H5)] has been studied by variable temperature 19F NMR spectroscopy and two processes detected. The first involves rapid exchange between two isomeric forms and is ascribed to inversion at either the sulphur or the {\ss}-carbon of the C(CF3)C(CF3)C(R?)=C(R')SR ligand. The second appears to involve restricted rotation of the CF3 attached to the {\ss}-carbon. {\textcopyright} 1991.",

author = "L. Carlton and Agh-Atabay, \{Naz M.\} and Davidson, \{Jack L.\}",

year = "1991",

month = aug,

day = "7",

language = "English",

volume = "413",

pages = "205--221",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-3",

}

TY - JOUR

T1 - Reactions of molybdenum and tungsten η2-C,C-vinyl complexes [Mη3-C(CF3)C(CF3)SR(CF3CCCF3)(η5-C5H5)] with alkynes leading to novel metallacycles

AU - Carlton, L.

AU - Agh-Atabay, Naz M.

AU - Davidson, Jack L.

PY - 1991/8/7

Y1 - 1991/8/7

N2 - The reactions of [M?3-C(CF3)C(CF3)SR(CF3C=CCF3)(?5-C5H5)](M = Mo, R = iPr; M = W, R = Me, iPr, tBu) with alkynes R'C=CR?, (R' = R? = Me, Et, Ph; R' = Ph, R? = Me) gives isomeric ?2-vinyl [M?3-C(CF3)C(CF3)C(R?)=C(R')(SR)(CF3C=CCF3)(?5-C5H5)] and/or ?4-butadienyl complexes [M?4-C(CF3)C(CF3)=C(R?)C(R')(SR)(CF3C=CCF3)(?5-C5H5)] (not all cases) apparently as a result of insertion of the incoming alkyne into the CS bond of the ?3-C(CF3)C(CF3)SR ligand. Thermolysis of [W?3-C(CF3)C(CF3)C(Me)=C(Ph)SiPr(CF3C=CCF3)(?5-C5H5)] in hexane at 55°C gives [WSiPr?5-C(CF3)C(CF3)C(CF3)C(CF3)C(Me)C(Ph)(?5-C5H5)]. In contrast thermolysis of [Mo?3-C(CF3)C(CF3)C(Me)=C(Me)SiPr(CF3C=CCF3)(?5-C5H5)] in hexane at 70°C gives [Mo?4-C(Me)C(Me)=C(CF3)C(CF3)(H)(CF3C=CCF3)(?5-C5H5)] via the intermediate [Mo?4-C(CF3)C(CF3)=C(Me)C(Me)SiPr(CF3C=CCF3)(?5-C5H5)]. Fluxional behaviour in complexes [M?3-C(CF3)C(CF3)C(R?)=C(R')(SR)(CF3C=CCF3)(?5-C5H5)] has been studied by variable temperature 19F NMR spectroscopy and two processes detected. The first involves rapid exchange between two isomeric forms and is ascribed to inversion at either the sulphur or the ß-carbon of the C(CF3)C(CF3)C(R?)=C(R')SR ligand. The second appears to involve restricted rotation of the CF3 attached to the ß-carbon. © 1991.

AB - The reactions of [M?3-C(CF3)C(CF3)SR(CF3C=CCF3)(?5-C5H5)](M = Mo, R = iPr; M = W, R = Me, iPr, tBu) with alkynes R'C=CR?, (R' = R? = Me, Et, Ph; R' = Ph, R? = Me) gives isomeric ?2-vinyl [M?3-C(CF3)C(CF3)C(R?)=C(R')(SR)(CF3C=CCF3)(?5-C5H5)] and/or ?4-butadienyl complexes [M?4-C(CF3)C(CF3)=C(R?)C(R')(SR)(CF3C=CCF3)(?5-C5H5)] (not all cases) apparently as a result of insertion of the incoming alkyne into the CS bond of the ?3-C(CF3)C(CF3)SR ligand. Thermolysis of [W?3-C(CF3)C(CF3)C(Me)=C(Ph)SiPr(CF3C=CCF3)(?5-C5H5)] in hexane at 55°C gives [WSiPr?5-C(CF3)C(CF3)C(CF3)C(CF3)C(Me)C(Ph)(?5-C5H5)]. In contrast thermolysis of [Mo?3-C(CF3)C(CF3)C(Me)=C(Me)SiPr(CF3C=CCF3)(?5-C5H5)] in hexane at 70°C gives [Mo?4-C(Me)C(Me)=C(CF3)C(CF3)(H)(CF3C=CCF3)(?5-C5H5)] via the intermediate [Mo?4-C(CF3)C(CF3)=C(Me)C(Me)SiPr(CF3C=CCF3)(?5-C5H5)]. Fluxional behaviour in complexes [M?3-C(CF3)C(CF3)C(R?)=C(R')(SR)(CF3C=CCF3)(?5-C5H5)] has been studied by variable temperature 19F NMR spectroscopy and two processes detected. The first involves rapid exchange between two isomeric forms and is ascribed to inversion at either the sulphur or the ß-carbon of the C(CF3)C(CF3)C(R?)=C(R')SR ligand. The second appears to involve restricted rotation of the CF3 attached to the ß-carbon. © 1991.

UR - https://www.scopus.com/pages/publications/0011591052

M3 - Article

SN - 0022-328X

VL - 413

SP - 205

EP - 221

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-3

ER -

Reactions of molybdenum and tungsten η²-C,C-vinyl complexes [Mη³-C(CF₃)C(CF₃)SR(CF₃CCCF₃)(η⁵-C₅H₅)] with alkynes leading to novel metallacycles

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