Abstract
Titanocene dichloride, [Ti]Cl-2 (1) ([Ti] = Ti(eta(5)-C5H4SiMe3)(2)), with one equiv. of the lithium thiolates LiSCHR-2-(C4H3S)-C-c (2a, R = H; 2b, R = Me) gave the appropriate [Ti](Cl)(SCHR-2-(C4H3S)-C-c) compounds (3a, R = H; 3b, R = Me) under mild reaction conditions. Further treatment of 3a,b with another equiv. of thiolates 2a,b produced the respective bis(thiolates) species [Ti](SCHR-2-(C4H3S)-C-c)(2) (4a,b). Titanocenes 4a,b are also accessible, when 1 is reacted with 2a,b in a 1:2 M ratio. The hydrolysis reaction of 4a,b produced the titanoxane cluster 5, consisting of a [Ti'](6)O-9 cage ([Ti'] = Ti(eta(5)-O5H4 SiMe3)) with a silsesquioxane analog structure. The molecular structure of 5 in the solid state is the first example of a trigonal prismatic Ti-6 polyhedron. Upon treatment of 4a,b with MCl2 (M = Pd, Pt), aiming to obtain heterobimetallic coordination complexes, however, either 1 or 3a,b were formed, depending on the reaction conditions. All the compounds have been characterized by elemental analysis, IR, NMR (H-1, C-13{H-1}) spectroscopy and mass-spectrometry. (C) 2018 Elsevier Ltd. All rights reserved.
| Original language | English |
|---|---|
| Pages (from-to) | 70-75 |
| Number of pages | 6 |
| Journal | Polyhedron |
| Volume | 148 |
| DOIs | |
| Publication status | Published - 1 Jul 2018 |
| Externally published | Yes |
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Titanocene thiolates [Ti]Cl(SCHR-2-(C4H3S)-C-c) and [Ti](SCHR-2-(C4H3S)-C-c)(2) (R = H, Me) : Synthesis, properties and reaction chemistry. / Taher, Deeb; Klaib, Sami; Stein, Thomas; Korb, Marcus; Rheinwald, Gerd; Ghazzy, Asma; Lang, Heinrich.
In: Polyhedron, Vol. 148, 01.07.2018, p. 70-75.Research output: Contribution to journal › Article
TY - JOUR
T1 - Titanocene thiolates [Ti]Cl(SCHR-2-(C4H3S)-C-c) and [Ti](SCHR-2-(C4H3S)-C-c)(2) (R = H, Me)
T2 - Synthesis, properties and reaction chemistry
AU - Taher, Deeb
AU - Klaib, Sami
AU - Stein, Thomas
AU - Korb, Marcus
AU - Rheinwald, Gerd
AU - Ghazzy, Asma
AU - Lang, Heinrich
PY - 2018/7/1
Y1 - 2018/7/1
N2 - Titanocene dichloride, [Ti]Cl-2 (1) ([Ti] = Ti(eta(5)-C5H4SiMe3)(2)), with one equiv. of the lithium thiolates LiSCHR-2-(C4H3S)-C-c (2a, R = H; 2b, R = Me) gave the appropriate [Ti](Cl)(SCHR-2-(C4H3S)-C-c) compounds (3a, R = H; 3b, R = Me) under mild reaction conditions. Further treatment of 3a,b with another equiv. of thiolates 2a,b produced the respective bis(thiolates) species [Ti](SCHR-2-(C4H3S)-C-c)(2) (4a,b). Titanocenes 4a,b are also accessible, when 1 is reacted with 2a,b in a 1:2 M ratio. The hydrolysis reaction of 4a,b produced the titanoxane cluster 5, consisting of a [Ti'](6)O-9 cage ([Ti'] = Ti(eta(5)-O5H4 SiMe3)) with a silsesquioxane analog structure. The molecular structure of 5 in the solid state is the first example of a trigonal prismatic Ti-6 polyhedron. Upon treatment of 4a,b with MCl2 (M = Pd, Pt), aiming to obtain heterobimetallic coordination complexes, however, either 1 or 3a,b were formed, depending on the reaction conditions. All the compounds have been characterized by elemental analysis, IR, NMR (H-1, C-13{H-1}) spectroscopy and mass-spectrometry. (C) 2018 Elsevier Ltd. All rights reserved.
AB - Titanocene dichloride, [Ti]Cl-2 (1) ([Ti] = Ti(eta(5)-C5H4SiMe3)(2)), with one equiv. of the lithium thiolates LiSCHR-2-(C4H3S)-C-c (2a, R = H; 2b, R = Me) gave the appropriate [Ti](Cl)(SCHR-2-(C4H3S)-C-c) compounds (3a, R = H; 3b, R = Me) under mild reaction conditions. Further treatment of 3a,b with another equiv. of thiolates 2a,b produced the respective bis(thiolates) species [Ti](SCHR-2-(C4H3S)-C-c)(2) (4a,b). Titanocenes 4a,b are also accessible, when 1 is reacted with 2a,b in a 1:2 M ratio. The hydrolysis reaction of 4a,b produced the titanoxane cluster 5, consisting of a [Ti'](6)O-9 cage ([Ti'] = Ti(eta(5)-O5H4 SiMe3)) with a silsesquioxane analog structure. The molecular structure of 5 in the solid state is the first example of a trigonal prismatic Ti-6 polyhedron. Upon treatment of 4a,b with MCl2 (M = Pd, Pt), aiming to obtain heterobimetallic coordination complexes, however, either 1 or 3a,b were formed, depending on the reaction conditions. All the compounds have been characterized by elemental analysis, IR, NMR (H-1, C-13{H-1}) spectroscopy and mass-spectrometry. (C) 2018 Elsevier Ltd. All rights reserved.
KW - Titanocene
KW - Thiolate
KW - Thiophene
KW - Titanoxane cluster
KW - Solid state structure
KW - ELECTROCHEMISTRY
KW - METALLOCENES
KW - FERROCENYL
KW - COMPLEXES
U2 - 10.1016/j.poly.2018.03.029
DO - 10.1016/j.poly.2018.03.029
M3 - Article
VL - 148
SP - 70
EP - 75
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
ER -