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Lookup NU author(s): Dr Keith Izod, Claire Jones, Dr Ross Harrington, Dr Paul Waddell
This is the authors' accepted manuscript of an article that has been published in its final definitive form by American Chemical Society , 2017.
For re-use rights please refer to the publisher's terms and conditions.
The hybrid alkyl/cyclopentadienyl “constrained-geometry” proligands (Me3Si)2CH{SiMe2(C5H5)}, (Me3Si)2CH{SiMe2(C5Me4H)} and (Me3Si)2CH{SiMe2(C5H4-3-SiMe3)} are synthesized by the reaction of the bromosilane (Me3Si)2CH(SiMe2Br) with the corresponding lithium cyclopentadienide. Metalation of these proligands with an excess of MeK gives access to the corresponding dipotassium salts [(Me3Si)2C{SiMe2(C5H4)}]K2(OEt2)0.5, [(Me3Si)2C{SiMe2(C5Me4)}]K2(OEt2) and [[(Me3Si)2C{SiMe2(C5H3-3-SiMe3)}]K2(C6H6)]2.2C6H6, after recrystallization. Similarly, the reaction between the phosphine-borane-substituted chlorosilane (Me3Si)CH{PMe2(BH3)}(SiMe2Cl) and [C5Me4H]Li gives the proligand (Me3Si)CH{PMe2(BH3)}{SiMe2(C5Me4H)}, which reacts with two equivalents of PhCH2K to give the dipotassium salt [(Me3Si)C{PMe2(BH3)}{SiMe2(C5Me4)}]K2(THF). X-ray crystallography reveals that the dipotassium salts of these hybrid ligands crystallize as zig-zag polymers or three-dimensional networks. The suitability of the dipotassium salts as ligand transfer reagents for the synthesis of lanthanide complexes was probed through the synthesis of the lanthanum(III) complex [(Me3Si)2C{SiMe2(C5Me4)}]La(I)(THF)2, in which the dianionic ligand chelates the lanthanum center.
Author(s): Izod K, Jones CF, Wildman EP, Harrington RW, Waddell PG
Publication type: Article
Publication status: Published
Journal: Organometallics
Year: 2017
Volume: 36
Issue: 21
Pages: 4238-4245
Print publication date: 13/11/2017
Online publication date: 30/10/2017
Acceptance date: 17/10/2017
Date deposited: 27/10/2017
ISSN (print): 0276-7333
ISSN (electronic): 1520-6041
Publisher: American Chemical Society
URL: https://doi.org/10.1021/acs.organomet.7b00662
DOI: 10.1021/acs.organomet.7b00662
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