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
SN - 0276-7333
VL - 24
SP - 1134
EP - 1144
JO - Organometallics
JF - Organometallics
IS - 6
ER -