Main Group Chemistry Laboratories, School of Chemistry, Bedson Building, University of Newcastle, Newcastle upon Tyne, UK NE1 7RU.
Dalton Trans. 2010 Aug 7;39(29):6705-9. doi: 10.1039/c001468k. Epub 2010 May 17.
The reaction between two equivalents of the potassium salt [(Me(3)Si)(2){Me(2)P(BH(3))}C]K (4) and SmI(2)(THF)(2) in refluxing THF yields the dialkylsamarium(II) compounds (Me(3)Si)(2){Me(2)P(BH(3))}CSm(THF) (5a) or (Me(3)Si)(2){Me(2)P(BH(3))}CSm(THF)(3) (5b), depending on the crystallisation conditions, in good yield as air- and moisture-sensitive crystalline solids. X-ray crystallography shows that, whereas both alkyl ligands chelate the samarium(II) ion in 5a, in 5b one alkyl ligand chelates the metal centre and one binds the metal only through its borane hydrogen atoms. The reaction between YbI(2) and two equivalents of 4 in refluxing benzene yields the solvent-free dialkylytterbium(II) compound (Me(3)Si)(2){Me(2)P(BH(3))}CYb (8). In contrast to 5a and 5b, compound 8 reacts rapidly with THF to give the free phosphine-borane (Me(3)Si)(2){Me(2)P(BH(3))}CH as the only identifiable product.
两当量的钾盐[(Me(3)Si)(2){Me(2)P(BH(3))}C]K(4)与 SmI(2)(THF)(2)在回流的 THF 中反应,生成二烷基钐(II)化合物(Me(3)Si)(2){Me(2)P(BH(3))}CSm(THF)(5a)或(Me(3)Si)(2){Me(2)P(BH(3))}CSm(THF)(3)(5b),具体取决于结晶条件,产率良好,为对空气和潮气敏感的结晶固体。X 射线晶体学表明,虽然在 5a 中两个烷基配体都螯合钐(II)离子,但在 5b 中一个烷基配体螯合金属中心,另一个仅通过其硼烷氢原子与金属结合。YbI(2)与两当量 4 在回流苯中反应,生成无溶剂的二烷基 ytterbium(II)化合物(Me(3)Si)(2){Me(2)P(BH(3))}CYb(8)。与 5a 和 5b 不同,化合物 8 与 THF 迅速反应,生成游离的膦硼烷(Me(3)Si)(2){Me(2)P(BH(3))}CH 作为唯一可识别的产物。