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A Suite of Sterically-Demanding Hybrid Alkyl/Cyclopentadienyl Ligands

Lookup NU author(s): Dr Keith Izod, Claire Jones, Dr Ross Harrington, Dr Paul Waddell

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This is the authors' accepted manuscript of an article that has been published in its final definitive form by American Chemical Society , 2017.

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Abstract

The hybrid alkyl/cyclopentadienyl “constrained-geometry” proligands (Me3Si)2CH{SiMe2(C5H5)}, (Me3Si)2CH­{SiMe(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.


Publication metadata

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

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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