Synthesis and Reactions of Sterically Encumbered, Heteroleptic Lanthanum Phosphides. Structural Characterization of [{(Me<sub>3</sub>Si)<sub>2</sub>CH}- (C<sub>6</sub>H<sub>4</sub>-2-CH<sub>2</sub>NMe<sub>2</sub>)P]<sub>2</sub>La(OR) and [{(Me<sub>3</sub>Si)<sub>2</sub>CH}- (C<sub>6</sub>H<sub>4</sub>-2-CH<sub>2</sub>NMe<sub>2</sub>)P]La(THF)[P(C<sub>6</sub>H<sub>4</sub>-2-CH<sub>2</sub>NMe<sub>2</sub>)- {CH(SiMe<sub>3</sub>)(SiMe<sub>2</sub>CH<sub>2</sub>)}] [R = <i>i</i>-Pr, <i>t</i>-Bu]
作者:Keith Izod、Stephen T. Liddle、William McFarlane、William Clegg
DOI:10.1021/om0498798
日期:2004.5.1
and 2 equiv of R(C6H4-2-CH2NMe2)P}K gives the heteroleptic complex R(C6H4-2-CH2NMe2)P}2LaI (1), which reacts in situ with 1 equiv of KOR‘ to give the corresponding mixed phosphide/alkoxide complexes R(C6H4-2-CH2NMe2)P}2La(OR‘) [R = (Me3Si)2CH, R‘ = t-Bu (2), i-Pr (3)]. A similar in situ reaction between 1 and 1 equiv of any of the alkali metal organometallics R‘K [R‘ = PhCH2, Me3SiCH2, (Me3Si)2CH]
R(C 6 H 4 -2-CH 2 NMe 2)P} K在LaI 3和2当量之间的复分解得到杂配体R(C 6 H 4 -2-CH 2 NMe 2)P} 2 LaI(1),它与1当量的KOR'原位反应,得到相应的混合磷化物/醇盐配合物R(C 6 H 4 -2-CH 2 NMe 2)P} 2 La(OR')[R =(Me 3 Si)2 CH,R'= t -Bu(2),i -Pr(3)]。碱金属有机金属R'K [R'= PhCH 2,Me 3 SiCH 2,(Me 3 Si)2 CH]中的1和1当量之间进行类似的原位反应,得到环金属化产物([[Me 3 Si ] 2 CH)(C 6 H 4 -2-CH 2 NMe 2)P} La(THF)[P(C 6 H 4 -2-CH 2 NMe 2)[CH SiMe 3 } SiMe 2 CH 2 } ](4)和R'H。均质三(烷基)(Me3 Si)2
Isolation and structural characterisation of two sterically crowded diphosphanes
Under specific conditions the reduction of the chlorophosphanes R(Me2NCH2-2-C6H4)PCI or RPCl2 [R = (Me3Si)(2)CH] with LiAlH4 gives the diphosphanes R(Me2NCH2-2-C6H4)P}(2) (2) and RPH-PHR (3), respectively in moderate to good yields. Compound 2 may be obtained in higher yield from the reaction of R(Me2NCH2-2-C6H4)P}Li with PbI2. Compounds 2 and 3 have been characterised by multi-element NMR spectroscopy and the meso-diastereomers of both compounds have been characterised by X-ray crystallography. In the solid state both meso-2 and meso-3 adopt an antiperiplanar conformation. (C) 2002 Elsevier Science B.V. All rights reserved.
Clegg, William; Doherty, Simon; Izod, Keith, Journal of the Chemical Society, Dalton Transactions, 1999, # 11, p. 1825 - 1829
作者:Clegg, William、Doherty, Simon、Izod, Keith、Kagerer, Hartmut、O'Shaughnessy, Paul、Sheffield, Joanne M.