Synthesis, characterization, and alkyne cyclotrimerization chemistry of titanium complexes supported by calixarene-derived bis(aryloxide) ligation

Folami T. Ladipo; Vallipuram Sarveswaran; Jesudoss V. Kingston; Rebecca A. Huyck; S. Y.Sergei Y. Bylikin; Shana D. Carr; Randy Watts; Sean Parkin

doi:10.1016/j.jorganchem.2003.10.039

Synthesis, characterization, and alkyne cyclotrimerization chemistry of titanium complexes supported by calixarene-derived bis(aryloxide) ligation

Folami T. Ladipo, Vallipuram Sarveswaran, Jesudoss V. Kingston, Rebecca A. Huyck, S. Y.Sergei Y. Bylikin, Shana D. Carr, Randy Watts, Sean Parkin

Chemistry

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

46 Scopus citations

Abstract

Proximally bridged calix[4]arene compounds (DESC)H₂ (3), (DMSHC)H₂ (4), (DMSMC)H₂ (5), and (DPSC)H₂ (6), in which one R₂Si group (R=alkyl or aryl) bridges adjacent oxygens, were synthesized via reaction between dialkyl- or diaryldichlorosilane and the corresponding calix[4]arene. Treatment of p- tert -butylcalix[4]arene with Ph₂SiCl₂ at room temperature or (o-MeC₆ H₄)₂SiCl₂ at 80 °C gave (ClPh₂SiCl)₂Calix-H₂ (7) and (o-Tol₂SiCl)₂Calix-H₂ (8), respectively. Titanium dichloride complexes 9-12 (L₂ TiCl₂, where L₂=DESC, DMSHC, DMSMC, or DPSC) were prepared in high yield from reaction of 3-6 with TiCl₄. The molecular structures of 7 and 12 were established by single-crystal X-ray diffraction studies. Reduction of 9, 11, and 12 with activated magnesium (Mg*) in the presence of an excess of Me₃SiC≡CH produced titananorbornadiene complexes L₂Ti{η⁶-1,2,4-C₆H₃ (SiMe₃)₃} (13-15, L₂=DESC, DMSMC, or DPSC), which were characterized in solution. Catalytic cyclotrimerization of both terminal and internal alkynes was achieved using catalyst systems derived from L₂TiCl₂ complexes 9-12 and Mg*. For unsymmetrically substituted internal alkynes, preference for 1,2,4-substitution decreased as the size difference of the substituent groups decreased. The cyclotrimerization of PhC≡CMe was more facile when the calixarene-derived bis(aryloxide) ligand was DPSC versus DMSMC, suggesting that the DPSC ligand may provide a less crowded titanium center and exert greater kinetic control over the course of the cyclotrimerization.

Original language	English
Pages (from-to)	502-514
Number of pages	13
Journal	Journal of Organometallic Chemistry
Volume	689
Issue number	3
DOIs	https://doi.org/10.1016/j.jorganchem.2003.10.039
State	Published - Feb 9 2004

Bibliographical note

Funding Information:
Thanks are expressed to the US National Science Foundation (Grant No. CHE-9984776) for financial support of this work. NMR instruments utilized in this research were funded in part by the CRIF program of the US National Science Foundation (Grant No. CHE-9974810). Thanks are expressed to Professor Carl Hertzel (Transylvania University) for recruitment of R.A. Huyck, and to Mr. Marc Maynor for his help with mass spectral data.

Keywords

Alkyne cyclotrimerization
Calixarene compounds
Reduced titanium
Titanium(IV)

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.jorganchem.2003.10.039

Cite this

Ladipo, F. T., Sarveswaran, V., Kingston, J. V., Huyck, R. A., Bylikin, S. Y. S. Y., Carr, S. D., Watts, R., & Parkin, S. (2004). Synthesis, characterization, and alkyne cyclotrimerization chemistry of titanium complexes supported by calixarene-derived bis(aryloxide) ligation. Journal of Organometallic Chemistry, 689(3), 502-514. https://doi.org/10.1016/j.jorganchem.2003.10.039

@article{c609805846b4497f9665c52437aba900,

title = "Synthesis, characterization, and alkyne cyclotrimerization chemistry of titanium complexes supported by calixarene-derived bis(aryloxide) ligation",

abstract = "Proximally bridged calix[4]arene compounds (DESC)H2 (3), (DMSHC)H2 (4), (DMSMC)H2 (5), and (DPSC)H2 (6), in which one R2Si group (R=alkyl or aryl) bridges adjacent oxygens, were synthesized via reaction between dialkyl- or diaryldichlorosilane and the corresponding calix[4]arene. Treatment of p- tert -butylcalix[4]arene with Ph2SiCl2 at room temperature or (o-MeC6 H4)2SiCl2 at 80 °C gave (ClPh2SiCl)2Calix-H2 (7) and (o-Tol2SiCl)2Calix-H2 (8), respectively. Titanium dichloride complexes 9-12 (L2 TiCl2, where L2=DESC, DMSHC, DMSMC, or DPSC) were prepared in high yield from reaction of 3-6 with TiCl4. The molecular structures of 7 and 12 were established by single-crystal X-ray diffraction studies. Reduction of 9, 11, and 12 with activated magnesium (Mg*) in the presence of an excess of Me3SiC≡CH produced titananorbornadiene complexes L2Ti{η6-1,2,4-C6H3 (SiMe3)3} (13-15, L2=DESC, DMSMC, or DPSC), which were characterized in solution. Catalytic cyclotrimerization of both terminal and internal alkynes was achieved using catalyst systems derived from L2TiCl2 complexes 9-12 and Mg*. For unsymmetrically substituted internal alkynes, preference for 1,2,4-substitution decreased as the size difference of the substituent groups decreased. The cyclotrimerization of PhC≡CMe was more facile when the calixarene-derived bis(aryloxide) ligand was DPSC versus DMSMC, suggesting that the DPSC ligand may provide a less crowded titanium center and exert greater kinetic control over the course of the cyclotrimerization.",

keywords = "Alkyne cyclotrimerization, Calixarene compounds, Reduced titanium, Titanium(IV)",

author = "Ladipo, {Folami T.} and Vallipuram Sarveswaran and Kingston, {Jesudoss V.} and Huyck, {Rebecca A.} and Bylikin, {S. Y.Sergei Y.} and Carr, {Shana D.} and Randy Watts and Sean Parkin",

note = "Funding Information: Thanks are expressed to the US National Science Foundation (Grant No. CHE-9984776) for financial support of this work. NMR instruments utilized in this research were funded in part by the CRIF program of the US National Science Foundation (Grant No. CHE-9974810). Thanks are expressed to Professor Carl Hertzel (Transylvania University) for recruitment of R.A. Huyck, and to Mr. Marc Maynor for his help with mass spectral data.",

year = "2004",

month = feb,

day = "9",

doi = "10.1016/j.jorganchem.2003.10.039",

language = "English",

volume = "689",

pages = "502--514",

number = "3",

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Ladipo, FT, Sarveswaran, V, Kingston, JV, Huyck, RA, Bylikin, SYSY, Carr, SD, Watts, R & Parkin, S 2004, 'Synthesis, characterization, and alkyne cyclotrimerization chemistry of titanium complexes supported by calixarene-derived bis(aryloxide) ligation', Journal of Organometallic Chemistry, vol. 689, no. 3, pp. 502-514. https://doi.org/10.1016/j.jorganchem.2003.10.039

Synthesis, characterization, and alkyne cyclotrimerization chemistry of titanium complexes supported by calixarene-derived bis(aryloxide) ligation. / Ladipo, Folami T.; Sarveswaran, Vallipuram; Kingston, Jesudoss V. et al.
In: Journal of Organometallic Chemistry, Vol. 689, No. 3, 09.02.2004, p. 502-514.

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

TY - JOUR

T1 - Synthesis, characterization, and alkyne cyclotrimerization chemistry of titanium complexes supported by calixarene-derived bis(aryloxide) ligation

AU - Ladipo, Folami T.

AU - Sarveswaran, Vallipuram

AU - Kingston, Jesudoss V.

AU - Huyck, Rebecca A.

AU - Bylikin, S. Y.Sergei Y.

AU - Carr, Shana D.

AU - Watts, Randy

AU - Parkin, Sean

N1 - Funding Information: Thanks are expressed to the US National Science Foundation (Grant No. CHE-9984776) for financial support of this work. NMR instruments utilized in this research were funded in part by the CRIF program of the US National Science Foundation (Grant No. CHE-9974810). Thanks are expressed to Professor Carl Hertzel (Transylvania University) for recruitment of R.A. Huyck, and to Mr. Marc Maynor for his help with mass spectral data.

PY - 2004/2/9

Y1 - 2004/2/9

N2 - Proximally bridged calix[4]arene compounds (DESC)H2 (3), (DMSHC)H2 (4), (DMSMC)H2 (5), and (DPSC)H2 (6), in which one R2Si group (R=alkyl or aryl) bridges adjacent oxygens, were synthesized via reaction between dialkyl- or diaryldichlorosilane and the corresponding calix[4]arene. Treatment of p- tert -butylcalix[4]arene with Ph2SiCl2 at room temperature or (o-MeC6 H4)2SiCl2 at 80 °C gave (ClPh2SiCl)2Calix-H2 (7) and (o-Tol2SiCl)2Calix-H2 (8), respectively. Titanium dichloride complexes 9-12 (L2 TiCl2, where L2=DESC, DMSHC, DMSMC, or DPSC) were prepared in high yield from reaction of 3-6 with TiCl4. The molecular structures of 7 and 12 were established by single-crystal X-ray diffraction studies. Reduction of 9, 11, and 12 with activated magnesium (Mg*) in the presence of an excess of Me3SiC≡CH produced titananorbornadiene complexes L2Ti{η6-1,2,4-C6H3 (SiMe3)3} (13-15, L2=DESC, DMSMC, or DPSC), which were characterized in solution. Catalytic cyclotrimerization of both terminal and internal alkynes was achieved using catalyst systems derived from L2TiCl2 complexes 9-12 and Mg*. For unsymmetrically substituted internal alkynes, preference for 1,2,4-substitution decreased as the size difference of the substituent groups decreased. The cyclotrimerization of PhC≡CMe was more facile when the calixarene-derived bis(aryloxide) ligand was DPSC versus DMSMC, suggesting that the DPSC ligand may provide a less crowded titanium center and exert greater kinetic control over the course of the cyclotrimerization.

AB - Proximally bridged calix[4]arene compounds (DESC)H2 (3), (DMSHC)H2 (4), (DMSMC)H2 (5), and (DPSC)H2 (6), in which one R2Si group (R=alkyl or aryl) bridges adjacent oxygens, were synthesized via reaction between dialkyl- or diaryldichlorosilane and the corresponding calix[4]arene. Treatment of p- tert -butylcalix[4]arene with Ph2SiCl2 at room temperature or (o-MeC6 H4)2SiCl2 at 80 °C gave (ClPh2SiCl)2Calix-H2 (7) and (o-Tol2SiCl)2Calix-H2 (8), respectively. Titanium dichloride complexes 9-12 (L2 TiCl2, where L2=DESC, DMSHC, DMSMC, or DPSC) were prepared in high yield from reaction of 3-6 with TiCl4. The molecular structures of 7 and 12 were established by single-crystal X-ray diffraction studies. Reduction of 9, 11, and 12 with activated magnesium (Mg*) in the presence of an excess of Me3SiC≡CH produced titananorbornadiene complexes L2Ti{η6-1,2,4-C6H3 (SiMe3)3} (13-15, L2=DESC, DMSMC, or DPSC), which were characterized in solution. Catalytic cyclotrimerization of both terminal and internal alkynes was achieved using catalyst systems derived from L2TiCl2 complexes 9-12 and Mg*. For unsymmetrically substituted internal alkynes, preference for 1,2,4-substitution decreased as the size difference of the substituent groups decreased. The cyclotrimerization of PhC≡CMe was more facile when the calixarene-derived bis(aryloxide) ligand was DPSC versus DMSMC, suggesting that the DPSC ligand may provide a less crowded titanium center and exert greater kinetic control over the course of the cyclotrimerization.

KW - Alkyne cyclotrimerization

KW - Calixarene compounds

KW - Reduced titanium

KW - Titanium(IV)

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DO - 10.1016/j.jorganchem.2003.10.039

M3 - Article

AN - SCOPUS:0742271375

SN - 0022-328X

VL - 689

SP - 502

EP - 514

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 3

ER -

Synthesis, characterization, and alkyne cyclotrimerization chemistry of titanium complexes supported by calixarene-derived bis(aryloxide) ligation

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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