Difluorenylsilanes, -germanes, and -stannanes exhibiting an unprecedented parallel arrangement of the fluorene units

G C Nemes, L Silaghi-Dumitrescu, I Silaghi-Dumitrescu, J Escudie, H Ranaivonjatovo, K C Molloy, M F Mahon, J Zukerman-Schpector

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

New, yet unprecedented molecular structures with parallel fluorene units were found by X-ray diffraction in (9,9'-disubstituted difluorenyl)(dimethyl) derivatives of group 14 elements Me2E(CR'R-2)(CR"R-2) (E = Si, R' = Me, R" = SiMe3, 6a; E = Ge, R' = Me, R" = SiMe3, 6b; and E = Sn, R' = R" = SiMe3, 5c; CR2 = fluorene units). This is in sharp contrast with the structure of monosubstituted Me2Ge(CHR2)(CR2-SiMe3) (3b) and disubstituted Me2E(CMeR2)(2) (E = Ge, 4b; E = Sn, 4c) derivatives where the two fluorene units are almost perpendicular. Intramolecular C-H(...)pi interactions are revealed by solution H-1 NMR spectroscopy and supported by the AM1 molecular orbital calculations. Intermolecular (aryl, alkyl)C-H(...)pi interactions leading to supramolecular associations are shown by the crystal structures of 3b, 4b, 4c, 5c, and 6a. In 4b and 5c rather unusual (CHHC)-H-... distances resembling the "dihydrogen" bonds are noticed. Synthesis, NMR spectra, and gas phase conformations predicted on the basis of AM1 semiempirical molecular orbital calculations are discussed for Me2E(CR'R-2)(CR"R-2) (E = Si, R' = R" = SiMe3, 5a; E = Ge, R' = R" = SiMe3, 5b; E = Sn, R' = H, R" = Me, 2c; R' = H, R" = SiMe3, 3c; R' = Me, R" = SiMe3, 6c; CR2 = fluorene units).
Original languageEnglish
Pages (from-to)1134-1144
Number of pages11
JournalOrganometallics
Volume24
Issue number6
DOIs
Publication statusPublished - 2005

Fingerprint

molecular orbitals
Orbital calculations
nuclear magnetic resonance
Molecular orbitals
molecular structure
interactions
vapor phases
Derivatives
crystal structure
synthesis
diffraction
Molecular structure
spectroscopy
Nuclear magnetic resonance spectroscopy
Conformations
x rays
Crystal structure
Gases
Nuclear magnetic resonance
X ray diffraction

Cite this

Nemes, G. C., Silaghi-Dumitrescu, L., Silaghi-Dumitrescu, I., Escudie, J., Ranaivonjatovo, H., Molloy, K. C., ... Zukerman-Schpector, J. (2005). Difluorenylsilanes, -germanes, and -stannanes exhibiting an unprecedented parallel arrangement of the fluorene units. Organometallics, 24(6), 1134-1144. https://doi.org/10.1021/om049543y

Difluorenylsilanes, -germanes, and -stannanes exhibiting an unprecedented parallel arrangement of the fluorene units. / Nemes, G C; Silaghi-Dumitrescu, L; Silaghi-Dumitrescu, I; Escudie, J; Ranaivonjatovo, H; Molloy, K C; Mahon, M F; Zukerman-Schpector, J.

In: Organometallics, Vol. 24, No. 6, 2005, p. 1134-1144.

Research output: Contribution to journalArticle

Nemes, GC, Silaghi-Dumitrescu, L, Silaghi-Dumitrescu, I, Escudie, J, Ranaivonjatovo, H, Molloy, KC, Mahon, MF & Zukerman-Schpector, J 2005, 'Difluorenylsilanes, -germanes, and -stannanes exhibiting an unprecedented parallel arrangement of the fluorene units', Organometallics, vol. 24, no. 6, pp. 1134-1144. https://doi.org/10.1021/om049543y
Nemes GC, Silaghi-Dumitrescu L, Silaghi-Dumitrescu I, Escudie J, Ranaivonjatovo H, Molloy KC et al. Difluorenylsilanes, -germanes, and -stannanes exhibiting an unprecedented parallel arrangement of the fluorene units. Organometallics. 2005;24(6):1134-1144. https://doi.org/10.1021/om049543y
Nemes, G C ; Silaghi-Dumitrescu, L ; Silaghi-Dumitrescu, I ; Escudie, J ; Ranaivonjatovo, H ; Molloy, K C ; Mahon, M F ; Zukerman-Schpector, J. / Difluorenylsilanes, -germanes, and -stannanes exhibiting an unprecedented parallel arrangement of the fluorene units. In: Organometallics. 2005 ; Vol. 24, No. 6. pp. 1134-1144.
@article{927ce5c6b18d46e6a21e7de770848763,
title = "Difluorenylsilanes, -germanes, and -stannanes exhibiting an unprecedented parallel arrangement of the fluorene units",
abstract = "New, yet unprecedented molecular structures with parallel fluorene units were found by X-ray diffraction in (9,9'-disubstituted difluorenyl)(dimethyl) derivatives of group 14 elements Me2E(CR'R-2)(CR{"}R-2) (E = Si, R' = Me, R{"} = SiMe3, 6a; E = Ge, R' = Me, R{"} = SiMe3, 6b; and E = Sn, R' = R{"} = SiMe3, 5c; CR2 = fluorene units). This is in sharp contrast with the structure of monosubstituted Me2Ge(CHR2)(CR2-SiMe3) (3b) and disubstituted Me2E(CMeR2)(2) (E = Ge, 4b; E = Sn, 4c) derivatives where the two fluorene units are almost perpendicular. Intramolecular C-H(...)pi interactions are revealed by solution H-1 NMR spectroscopy and supported by the AM1 molecular orbital calculations. Intermolecular (aryl, alkyl)C-H(...)pi interactions leading to supramolecular associations are shown by the crystal structures of 3b, 4b, 4c, 5c, and 6a. In 4b and 5c rather unusual (CHHC)-H-... distances resembling the {"}dihydrogen{"} bonds are noticed. Synthesis, NMR spectra, and gas phase conformations predicted on the basis of AM1 semiempirical molecular orbital calculations are discussed for Me2E(CR'R-2)(CR{"}R-2) (E = Si, R' = R{"} = SiMe3, 5a; E = Ge, R' = R{"} = SiMe3, 5b; E = Sn, R' = H, R{"} = Me, 2c; R' = H, R{"} = SiMe3, 3c; R' = Me, R{"} = SiMe3, 6c; CR2 = fluorene units).",
author = "Nemes, {G C} and L Silaghi-Dumitrescu and I Silaghi-Dumitrescu and J Escudie and H Ranaivonjatovo and Molloy, {K C} and Mahon, {M F} and J Zukerman-Schpector",
note = "ID number: ISI:000227533800016",
year = "2005",
doi = "10.1021/om049543y",
language = "English",
volume = "24",
pages = "1134--1144",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Difluorenylsilanes, -germanes, and -stannanes exhibiting an unprecedented parallel arrangement of the fluorene units

AU - Nemes, G C

AU - Silaghi-Dumitrescu, L

AU - Silaghi-Dumitrescu, I

AU - Escudie, J

AU - Ranaivonjatovo, H

AU - Molloy, K C

AU - Mahon, M F

AU - Zukerman-Schpector, J

N1 - ID number: ISI:000227533800016

PY - 2005

Y1 - 2005

N2 - New, yet unprecedented molecular structures with parallel fluorene units were found by X-ray diffraction in (9,9'-disubstituted difluorenyl)(dimethyl) derivatives of group 14 elements Me2E(CR'R-2)(CR"R-2) (E = Si, R' = Me, R" = SiMe3, 6a; E = Ge, R' = Me, R" = SiMe3, 6b; and E = Sn, R' = R" = SiMe3, 5c; CR2 = fluorene units). This is in sharp contrast with the structure of monosubstituted Me2Ge(CHR2)(CR2-SiMe3) (3b) and disubstituted Me2E(CMeR2)(2) (E = Ge, 4b; E = Sn, 4c) derivatives where the two fluorene units are almost perpendicular. Intramolecular C-H(...)pi interactions are revealed by solution H-1 NMR spectroscopy and supported by the AM1 molecular orbital calculations. Intermolecular (aryl, alkyl)C-H(...)pi interactions leading to supramolecular associations are shown by the crystal structures of 3b, 4b, 4c, 5c, and 6a. In 4b and 5c rather unusual (CHHC)-H-... distances resembling the "dihydrogen" bonds are noticed. Synthesis, NMR spectra, and gas phase conformations predicted on the basis of AM1 semiempirical molecular orbital calculations are discussed for Me2E(CR'R-2)(CR"R-2) (E = Si, R' = R" = SiMe3, 5a; E = Ge, R' = R" = SiMe3, 5b; E = Sn, R' = H, R" = Me, 2c; R' = H, R" = SiMe3, 3c; R' = Me, R" = SiMe3, 6c; CR2 = fluorene units).

AB - New, yet unprecedented molecular structures with parallel fluorene units were found by X-ray diffraction in (9,9'-disubstituted difluorenyl)(dimethyl) derivatives of group 14 elements Me2E(CR'R-2)(CR"R-2) (E = Si, R' = Me, R" = SiMe3, 6a; E = Ge, R' = Me, R" = SiMe3, 6b; and E = Sn, R' = R" = SiMe3, 5c; CR2 = fluorene units). This is in sharp contrast with the structure of monosubstituted Me2Ge(CHR2)(CR2-SiMe3) (3b) and disubstituted Me2E(CMeR2)(2) (E = Ge, 4b; E = Sn, 4c) derivatives where the two fluorene units are almost perpendicular. Intramolecular C-H(...)pi interactions are revealed by solution H-1 NMR spectroscopy and supported by the AM1 molecular orbital calculations. Intermolecular (aryl, alkyl)C-H(...)pi interactions leading to supramolecular associations are shown by the crystal structures of 3b, 4b, 4c, 5c, and 6a. In 4b and 5c rather unusual (CHHC)-H-... distances resembling the "dihydrogen" bonds are noticed. Synthesis, NMR spectra, and gas phase conformations predicted on the basis of AM1 semiempirical molecular orbital calculations are discussed for Me2E(CR'R-2)(CR"R-2) (E = Si, R' = R" = SiMe3, 5a; E = Ge, R' = R" = SiMe3, 5b; E = Sn, R' = H, R" = Me, 2c; R' = H, R" = SiMe3, 3c; R' = Me, R" = SiMe3, 6c; CR2 = fluorene units).

U2 - 10.1021/om049543y

DO - 10.1021/om049543y

M3 - Article

VL - 24

SP - 1134

EP - 1144

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 6

ER -