10.1021/ic961304i.s001
Shwu-Juian Lin
Shwu-Juian
Lin
Tay-Ning Hong
Tay-Ning
Hong
Jo-Yu Tung
Jo-Yu
Tung
Jyh-Horung Chen
Jyh-Horung
Chen
Molecular Structures of Ge(tpp)(OAc)<sub>2</sub> and In(tpp)(OAc) and Their Implications:
Correlations between the <sup>13</sup>C NMR Chemical Shift of the Acetato Ligand and Different
Types of Carboxylate Coordination in M(por)(OAc)<i><sub>n</sub></i> {por = tpp
(5,10,15,20-Tetraphenylporphyrinate), tmpp
(5,10,15,20-Tetrakis(4-methoxyphenyl)porphyrinate), tpyp
(5,10,15,20-Tetrakis(4-pyridyl)porphyrinate); M = Ga, In, Tl, Ge, Sn; <i>n</i> = 1, 2}
American Chemical Society
1997
13 C chemical shifts
Molecular Structures
Carboxylate Coordination
unidentate case
title compound
Different Types
germanium atom
13 C NMR Chemical Shift
Ge
Experimental results
apical site
acetato ligand
1.999 Å.
carbonyl carbons
13 C methyl
acetato group
octahedral coordination geometry
porphyrin plane
acetate groups
germanium center
13 C NMR data
crystal structure
chelating bidentate case
carbonyl chemical shifts
Acetato Ligand
bidentate OAc
carboxylate coordination
0.762 Å
coordination sphere
1997-08-27 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Molecular_Structures_of_Ge_tpp_OAc_sub_2_sub_and_In_tpp_OAc_and_Their_Implications_Correlations_between_the_sup_13_sup_C_NMR_Chemical_Shift_of_the_Acetato_Ligand_and_Different_Types_of_Carboxylate_Coordination_in_M_por_OAc_i_sub_n_sub_i_por_tpp_5_10_15_20/3617787
In this work, we determine the crystal structure of
bis(acetato)(<i>meso</i>-tetraphenylporphyrinato)germanium(III),
Ge(tpp)(OAc)<sub>2</sub>. Experimental results indicate
that the germanium atom has an octahedral coordination
geometry.
The geometry around the germanium center of the
Ge(tpp)(OAc)<sub>2</sub> molecule has Ge−O(1) =
1.874(5) Å and an
average Ge−N = 1.999 Å. The acetate groups are unidentately
coordinated to the germanium(IV) atom. In the
title compound,
(acetato)(<i>meso</i>-tetraphenylporphyrinato)indium(III),
In(tpp)(OAc), the coordination sphere of the
In<sup>3+</sup> ion is an approximately square-based pyramid in
which the apical site is occupied by an asymmetric
(chelating)
bidentate OAc<sup>-</sup> group. The average In−N bond
distance is 2.173(3) Å, and the In atom is displaced 0.762
Å
from the porphyrin plane. The In−O(1) and In−O(2) distances
are 2.322(4) and 2.215(4) Å, respectively.
To
develop the correlations between the <sup>13</sup>C chemical shifts of
the acetato ligand and types of carboxylate coordination,
this work also thoroughly examines the <sup>13</sup>C NMR data of the
methyl and carbonyl carbons on 13 acetato
porphyrinato metal complexes M(por)(OAc)<i><sub>n</sub></i>
with <i>n</i> = 1, 2, por = tpp, tmpp
(5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinate), tpyp
(5,10,15,20-tetrakis(4-pyridyl)porphyrinate),
and M = Ga, In, Tl, Ge, Sn. According to these
results, the <sup>13</sup>C methyl and carbonyl chemical shifts of the
acetato group at 24 °C are separately located at 20.5
± 0.2 and 168.2 ± 1.7 ppm for the acetate, which is unidentately
coordinated to the metal (<i>i.e.,</i> the unidentate
case) and at 18.0 ± 0.7 and 175.2 ± 1.6 ppm for the chelating
bidentate case.