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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



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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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

Date deposited: 27/10/2017

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society


DOI: 10.1021/acs.organomet.7b00662


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