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

Deeb Taher, Sami Klaib, Thomas Stein, Marcus Korb, Gerd Rheinwald, Asma Ghazzy, Heinrich Lang

Research output: Contribution to journalArticle

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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 languageEnglish
Pages (from-to)70-75
Number of pages6
JournalPolyhedron
Volume148
DOIs
Publication statusPublished - 1 Jul 2018
Externally publishedYes

Cite this

Taher, Deeb ; Klaib, Sami ; Stein, Thomas ; Korb, Marcus ; Rheinwald, Gerd ; Ghazzy, Asma ; Lang, Heinrich. / 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. In: Polyhedron. 2018 ; Vol. 148. pp. 70-75.
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title = "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",
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.",
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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 journalArticle

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 -