Izod Keith, Wills Corinne, Clegg William, Harrington Ross W
Main Group Chemistry Laboratories, Department of Chemistry, School of Natural Sciences, Bedson Building, University of Newcastle, Newcastle upon Tyne, UK, NE1 7RU.
Dalton Trans. 2007 Sep 7(33):3669-75. doi: 10.1039/b708279g. Epub 2007 Jul 5.
The adducts [(Me(3)Si)(2){Me(2)P(BH(3))}C]K(L)(n) [L = THF, n = 0.5, m = infinity (2a); L = tmeda (2b), pmdeta (2c), n = 1, m = 2] may be synthesised by treatment of solvent-free [(Me(3)Si)(2){Me(2)P(BH(3))}C]K (2) with the corresponding Lewis base (tmeda = N,N,N',N'-tetramethylethylenediamine; pmdeta = N,N,N',N'',N''-pentamethyldiethylenetriamine). X-Ray crystallography reveals that, whereas 2 crystallises with a complex 2-dimensional sheet structure, 2a crystallises as a ribbon-type one-dimensional polymer and both 2b and 2c crystallise as dimers. The corresponding complex with 12-crown-4, [K(12-crown-4)(2)][(Me(3)Si)(2){Me(2)P(BH(3))}C] (2d) crystallises as a separated ion pair. The complexes [(Me(3)Si)(2){Me(2)P(BH(3))}C]M(pmdeta) [M = Na, n = 1 (6); M = Rb, n = 2 (7)] may be synthesised by treatment of [(Me(3)Si)(2){Me(2)P(BH(3))}C]M with pmdeta. Whereas crystallises as a discrete monomer, compound 7 crystallises as a dimer. Compounds 2, 2a-2d, 6, 7 and the corresponding caesium derivative [(Me(3)Si)(2){Me(2)P(BH(3))}C]Cs(pmdeta) () provide an opportunity to consider the influence of the ionic radius of the metal and the nature of the co-ligands on the structures of alkali metal complexes of a phosphine-borane-stabilised carbanion.
加合物[(Me(3)Si)(2){Me(2)P(BH(3))}C]K(L)(n) [L = 四氢呋喃，n = 0.5，m = ∞ (2a)；L = 四甲基乙二胺 (2b)，五甲基二亚乙基三胺 (2c)，n = 1，m = 2] 可通过用相应的路易斯碱（四甲基乙二胺 = N,N,N',N'-四甲基乙二胺；五甲基二亚乙基三胺 = N,N,N',N'',N''-五甲基二亚乙基三胺）处理无溶剂的[(Me(3)Si)(2){Me(2)P(BH(3))}C]K (2) 来合成。X射线晶体学表明，虽然2以复杂的二维片状结构结晶，但2a以带状一维聚合物形式结晶，而2b和2c均以二聚体形式结晶。与12-冠-4形成的相应配合物[K(12-冠-4)(2)][(Me(3)Si)(2){Me(2)P(BH(3))}C] (2d) 以分离的离子对形式结晶。配合物[(Me(3)Si)(2){Me(2)P(BH(3))}C]M(五甲基二亚乙基三胺) [M = Na，n = 1 (6)；M = Rb，n = 2 (7)] 可通过用五甲基二亚乙基三胺处理[(Me(3)Si)(2){Me(2)P(BH(3))}C]M来合成。化合物6以离散单体形式结晶，而化合物7以二聚体形式结晶。化合物2、2a - 2d、6、7以及相应的铯衍生物[(Me(3)Si)(2){Me(2)P(BH(3))}C]Cs(五甲基二亚乙基三胺) () 提供了一个机会来考虑金属离子半径和共配体性质对膦硼烷稳定的碳负离子的碱金属配合物结构的影响。
