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A Suite of Sterically-Demanding Hybrid Alkyl/Cyclopentadienyl Ligands
Organometallics ( IF 2.8 ) Pub Date : 2017-10-30 00:00:00 , DOI: 10.1021/acs.organomet.7b00662
Keith Izod 1 , Claire F. Jones 1 , Elizabeth P. Wildman 1 , Ross W. Harrington 1 , Paul G. Waddell 1
Affiliation  

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.

中文翻译:

一套立体要求很​​高的烷基/环戊二烯基杂配体

杂烷基/环戊二烯基“约束几何”配体(Me 3 Si)2 CH {SiMe 2(C 5 H 5)},(Me 3 Si)2 CH {SiMe 2(C 5 Me 4 H)}和(Me通过溴硅烷(Me 3 Si)2 CH(SiMe 2)反应合成了3 Si)2 CH {SiMe 2(C 5 H 4 -3-SiMe 3)}Br)与相应的环戊二烯酸锂。这些配体与过量的MeK金属化可得到相应的二钾盐[(Me 3 Si)2 C {SiMe 2(C 5 H 4)}] K 2(OEt 20.5,[(Me 3 Si)2 C {SiMe 2(C 5 Me 4)}] K 2(OEt 2)和[[(Me 3 Si)2 C {SiMe 2(C 5 H 3 -3-SiMe 3)}] K 2(C6 H 6)] 2 ·2C 6 H 6重结晶后。同样,膦-硼烷取代的氯硅烷(Me 3 Si)CH {PMe 2(BH 3)}(SiMe 2 Cl)与[C 5 Me 4 H] Li之间的反应产生了配体(Me 3 Si)CH { PMe 2(BH 3)} {SiMe 2(C 5 Me 4 H)},它与2当量的PhCH 2 K反应生成二钾盐[(Me 3 Si)C {PMe 2(BH 3)} {SiMe2(C 5 Me 4)}] K 2(THF)。X射线晶体学显示这些杂化配体的双钾盐结晶为之字形聚合物或三维网络。通过镧(III)配合物[(Me 3 Si)2 C {SiMe 2(C 5 Me 4)}] La(I )(THF)2,其中双阴离子配体螯合镧中心。
更新日期:2017-10-31
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