Yttrium calix[4]arene complexes. Silylation and silylamine elimination reactions on model oxo surfaces

R. Anwander; J. Eppinger; I. Nagl; W. Scherer; M. Tafipolsky; P. Sirsch

doi:10.1021/ic000147r

Yttrium calix[4]arene complexes. Silylation and silylamine elimination reactions on model oxo surfaces

R. Anwander^*, J. Eppinger, I. Nagl, W. Scherer, M. Tafipolsky, P. Sirsch

^*Corresponding author for this work

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

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Abstract

The synthesis and the spectroscopic and structural characterization of lower-rim-silylated and rare-earth-metalated calix[4]arenes are presented. Hexamethyldisilazane, HN(SiMe₃)₂, reacted in a selective manner with [p-tert-butylcalix[4]arene]H₄ (1) in refluxing mesitylene to give the 1,3-silylated product [p-tert-butylcalix[4]arene(SiMe₃)₂]-H₂ (2) in high yield. The molecular structure of compound 2, as revealed by X-ray crystallography, shows the pinched cone conformation of the calixarene bowl, featuring hydrogen bonding between the phenylsilyl ether and phenolic oxygen atoms (O···O, 2.838 Å). From the reaction of the sterically more crowded tetraphenyldimethyldisilazane, HN(SiMePh₂)₂, only starting material could be recovered. In contrast, tetramethyldisilazane, HN-(SiHMe₂)₂, afforded the tetrakis-silylated product [p-tert-butylcalix[4]arene(SiHMe₂)₄] (3) in hexane solution at ambient temperature. A single-crystal X-ray diffraction study of compound 3 established the 1,2-alternate conformation, which is also present in solution, as indicated by ¹H NMR spectroscopy. The yttrium complex Y[N(SiHMe₂)₂]₃(THF)₂ (4) exchanged all of its silylamide ligands when treated with an equimolar amount of 1 in toluene at ambient temperature to yield compound 5, as indicated by IR and NMR spectroscopy. The molecular structure of 5 revealed a centrosymmetric dimer of composition [Y{p-tert-butylcalix[4]arene(SiHMe₂)}(THF)]₂. Three of the deprotonated phenolic oxygen atoms of the calixarene bowl bind to the metal center, two as terminal ligands and one in a bridging mode, while the fourth undergoes in situ silylation (v(SiH) 2127 cm^-1). The distorted-trigonal-bipyramidal coordination geometry is completed by a THF molecule. Bis-silylated 2 reacted with 4 to form the heteroleptic complex {Y[p-tert-butylcalix[4]arene(SiMe₃)₂][N(SiHMe₂)₂]} (6). Crystal data: C₅₀H₇₂O₄-Si₂ (2), triclinic, P1̄, a = 12.8914(3) Å, b = 14.9270(5) Å, c = 15.1652(4) Å, α = 77.293(2)°, β = 65.019(2)°, γ = 72.234(2)°, Z = 2; C₅₂H₈₀O₄Si₄ (3), triclinic, P1̄, a = 10.1774(2) Å, b = 14.1680(2) Å, c = 18.7206(2) Å, α = 95.8195(8)°, β = 95.5294(8)°, γ = 98.1098(7)°, Z = 2; C₁₀₀H₁₃₂O₁₀Si₂Y₂, 2(C₆H₆) (5), triclinic, P1̄, a = 13.2625(4) Å, b = 14.5894(3) Å, c = 17.0458(5) Å, α = 65.0986(14)°, β = 77.8786(8)°, γ = 85.5125(13)°, Z = 1.

Original language	English (US)
Pages (from-to)	4713-4720
Number of pages	8
Journal	Inorganic chemistry
Volume	39
Issue number	21
DOIs	https://doi.org/10.1021/ic000147r
State	Published - Oct 16 2000
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic000147r

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@article{8ddcb5f2129e4f6a997c05441a796d39,

title = "Yttrium calix[4]arene complexes. Silylation and silylamine elimination reactions on model oxo surfaces",

abstract = "The synthesis and the spectroscopic and structural characterization of lower-rim-silylated and rare-earth-metalated calix[4]arenes are presented. Hexamethyldisilazane, HN(SiMe3)2, reacted in a selective manner with [p-tert-butylcalix[4]arene]H4 (1) in refluxing mesitylene to give the 1,3-silylated product [p-tert-butylcalix[4]arene(SiMe3)2]-H2 (2) in high yield. The molecular structure of compound 2, as revealed by X-ray crystallography, shows the pinched cone conformation of the calixarene bowl, featuring hydrogen bonding between the phenylsilyl ether and phenolic oxygen atoms (O···O, 2.838 {\AA}). From the reaction of the sterically more crowded tetraphenyldimethyldisilazane, HN(SiMePh2)2, only starting material could be recovered. In contrast, tetramethyldisilazane, HN-(SiHMe2)2, afforded the tetrakis-silylated product [p-tert-butylcalix[4]arene(SiHMe2)4] (3) in hexane solution at ambient temperature. A single-crystal X-ray diffraction study of compound 3 established the 1,2-alternate conformation, which is also present in solution, as indicated by 1H NMR spectroscopy. The yttrium complex Y[N(SiHMe2)2]3(THF)2 (4) exchanged all of its silylamide ligands when treated with an equimolar amount of 1 in toluene at ambient temperature to yield compound 5, as indicated by IR and NMR spectroscopy. The molecular structure of 5 revealed a centrosymmetric dimer of composition [Y{p-tert-butylcalix[4]arene(SiHMe2)}(THF)]2. Three of the deprotonated phenolic oxygen atoms of the calixarene bowl bind to the metal center, two as terminal ligands and one in a bridging mode, while the fourth undergoes in situ silylation (v(SiH) 2127 cm-1). The distorted-trigonal-bipyramidal coordination geometry is completed by a THF molecule. Bis-silylated 2 reacted with 4 to form the heteroleptic complex {Y[p-tert-butylcalix[4]arene(SiMe3)2][N(SiHMe2)2]} (6). Crystal data: C50H72O4-Si2 (2), triclinic, P{\=1}, a = 12.8914(3) {\AA}, b = 14.9270(5) {\AA}, c = 15.1652(4) {\AA}, α = 77.293(2)°, β = 65.019(2)°, γ = 72.234(2)°, Z = 2; C52H80O4Si4 (3), triclinic, P{\=1}, a = 10.1774(2) {\AA}, b = 14.1680(2) {\AA}, c = 18.7206(2) {\AA}, α = 95.8195(8)°, β = 95.5294(8)°, γ = 98.1098(7)°, Z = 2; C100H132O10Si2Y2, 2(C6H6) (5), triclinic, P{\=1}, a = 13.2625(4) {\AA}, b = 14.5894(3) {\AA}, c = 17.0458(5) {\AA}, α = 65.0986(14)°, β = 77.8786(8)°, γ = 85.5125(13)°, Z = 1.",

author = "R. Anwander and J. Eppinger and I. Nagl and W. Scherer and M. Tafipolsky and P. Sirsch",

year = "2000",

month = oct,

day = "16",

doi = "10.1021/ic000147r",

language = "English (US)",

volume = "39",

pages = "4713--4720",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "21",

}

TY - JOUR

T1 - Yttrium calix[4]arene complexes. Silylation and silylamine elimination reactions on model oxo surfaces

AU - Anwander, R.

AU - Eppinger, J.

AU - Nagl, I.

AU - Scherer, W.

AU - Tafipolsky, M.

AU - Sirsch, P.

PY - 2000/10/16

Y1 - 2000/10/16

N2 - The synthesis and the spectroscopic and structural characterization of lower-rim-silylated and rare-earth-metalated calix[4]arenes are presented. Hexamethyldisilazane, HN(SiMe3)2, reacted in a selective manner with [p-tert-butylcalix[4]arene]H4 (1) in refluxing mesitylene to give the 1,3-silylated product [p-tert-butylcalix[4]arene(SiMe3)2]-H2 (2) in high yield. The molecular structure of compound 2, as revealed by X-ray crystallography, shows the pinched cone conformation of the calixarene bowl, featuring hydrogen bonding between the phenylsilyl ether and phenolic oxygen atoms (O···O, 2.838 Å). From the reaction of the sterically more crowded tetraphenyldimethyldisilazane, HN(SiMePh2)2, only starting material could be recovered. In contrast, tetramethyldisilazane, HN-(SiHMe2)2, afforded the tetrakis-silylated product [p-tert-butylcalix[4]arene(SiHMe2)4] (3) in hexane solution at ambient temperature. A single-crystal X-ray diffraction study of compound 3 established the 1,2-alternate conformation, which is also present in solution, as indicated by 1H NMR spectroscopy. The yttrium complex Y[N(SiHMe2)2]3(THF)2 (4) exchanged all of its silylamide ligands when treated with an equimolar amount of 1 in toluene at ambient temperature to yield compound 5, as indicated by IR and NMR spectroscopy. The molecular structure of 5 revealed a centrosymmetric dimer of composition [Y{p-tert-butylcalix[4]arene(SiHMe2)}(THF)]2. Three of the deprotonated phenolic oxygen atoms of the calixarene bowl bind to the metal center, two as terminal ligands and one in a bridging mode, while the fourth undergoes in situ silylation (v(SiH) 2127 cm-1). The distorted-trigonal-bipyramidal coordination geometry is completed by a THF molecule. Bis-silylated 2 reacted with 4 to form the heteroleptic complex {Y[p-tert-butylcalix[4]arene(SiMe3)2][N(SiHMe2)2]} (6). Crystal data: C50H72O4-Si2 (2), triclinic, P1̄, a = 12.8914(3) Å, b = 14.9270(5) Å, c = 15.1652(4) Å, α = 77.293(2)°, β = 65.019(2)°, γ = 72.234(2)°, Z = 2; C52H80O4Si4 (3), triclinic, P1̄, a = 10.1774(2) Å, b = 14.1680(2) Å, c = 18.7206(2) Å, α = 95.8195(8)°, β = 95.5294(8)°, γ = 98.1098(7)°, Z = 2; C100H132O10Si2Y2, 2(C6H6) (5), triclinic, P1̄, a = 13.2625(4) Å, b = 14.5894(3) Å, c = 17.0458(5) Å, α = 65.0986(14)°, β = 77.8786(8)°, γ = 85.5125(13)°, Z = 1.

AB - The synthesis and the spectroscopic and structural characterization of lower-rim-silylated and rare-earth-metalated calix[4]arenes are presented. Hexamethyldisilazane, HN(SiMe3)2, reacted in a selective manner with [p-tert-butylcalix[4]arene]H4 (1) in refluxing mesitylene to give the 1,3-silylated product [p-tert-butylcalix[4]arene(SiMe3)2]-H2 (2) in high yield. The molecular structure of compound 2, as revealed by X-ray crystallography, shows the pinched cone conformation of the calixarene bowl, featuring hydrogen bonding between the phenylsilyl ether and phenolic oxygen atoms (O···O, 2.838 Å). From the reaction of the sterically more crowded tetraphenyldimethyldisilazane, HN(SiMePh2)2, only starting material could be recovered. In contrast, tetramethyldisilazane, HN-(SiHMe2)2, afforded the tetrakis-silylated product [p-tert-butylcalix[4]arene(SiHMe2)4] (3) in hexane solution at ambient temperature. A single-crystal X-ray diffraction study of compound 3 established the 1,2-alternate conformation, which is also present in solution, as indicated by 1H NMR spectroscopy. The yttrium complex Y[N(SiHMe2)2]3(THF)2 (4) exchanged all of its silylamide ligands when treated with an equimolar amount of 1 in toluene at ambient temperature to yield compound 5, as indicated by IR and NMR spectroscopy. The molecular structure of 5 revealed a centrosymmetric dimer of composition [Y{p-tert-butylcalix[4]arene(SiHMe2)}(THF)]2. Three of the deprotonated phenolic oxygen atoms of the calixarene bowl bind to the metal center, two as terminal ligands and one in a bridging mode, while the fourth undergoes in situ silylation (v(SiH) 2127 cm-1). The distorted-trigonal-bipyramidal coordination geometry is completed by a THF molecule. Bis-silylated 2 reacted with 4 to form the heteroleptic complex {Y[p-tert-butylcalix[4]arene(SiMe3)2][N(SiHMe2)2]} (6). Crystal data: C50H72O4-Si2 (2), triclinic, P1̄, a = 12.8914(3) Å, b = 14.9270(5) Å, c = 15.1652(4) Å, α = 77.293(2)°, β = 65.019(2)°, γ = 72.234(2)°, Z = 2; C52H80O4Si4 (3), triclinic, P1̄, a = 10.1774(2) Å, b = 14.1680(2) Å, c = 18.7206(2) Å, α = 95.8195(8)°, β = 95.5294(8)°, γ = 98.1098(7)°, Z = 2; C100H132O10Si2Y2, 2(C6H6) (5), triclinic, P1̄, a = 13.2625(4) Å, b = 14.5894(3) Å, c = 17.0458(5) Å, α = 65.0986(14)°, β = 77.8786(8)°, γ = 85.5125(13)°, Z = 1.

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U2 - 10.1021/ic000147r

DO - 10.1021/ic000147r

M3 - Article

C2 - 11196944

AN - SCOPUS:0034675575

SN - 0020-1669

VL - 39

SP - 4713

EP - 4720

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 21

ER -

Yttrium calix[4]arene complexes. Silylation and silylamine elimination reactions on model oxo surfaces

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