3 years ago

A Suite of Sterically-Demanding Hybrid Alkyl/Cyclopentadienyl Ligands

A Suite of Sterically-Demanding Hybrid Alkyl/Cyclopentadienyl Ligands
Keith Izod, Elizabeth P. Wildman, Claire F. Jones, Paul G. Waddell, Ross W. Harrington
The hybrid alkyl/cyclopentadienyl “constrained-geometry” proligands (Me3Si)2CH{SiMe2(C5H5)}, (Me3Si)2CH{SiMe2(C5Me4H)} and (Me3Si)2CH{SiMe2(C5H4-3-SiMe3)} were synthesized by the reaction of the bromosilane (Me3Si)2CH(SiMe2Br) with the corresponding lithium cyclopentadienides. 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 2 equiv of PhCH2K to give the dipotassium salt [(Me3Si)C{PMe2(BH3)}{SiMe2(C5Me4)}]K2(THF). X-ray crystallography revealed that the dipotassium salts of these hybrid ligands crystallize as zigzag 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.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00662

DOI: 10.1021/acs.organomet.7b00662

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