Alkali metal complexes of sterically demanding amino-functionalised secondary phosphanide ligands
作者:Keith Izod、John C. Stewart、William Clegg、Ross W. Harrington
DOI:10.1039/b614373c
日期:——
The reaction between (Me(3)Si)(2)CH}PCl(2) (4) and one equivalent of either [C(6)H(4)-2-NMe(2)]Li or [2-C(5)H(4)N]ZnCl, followed by in situ reduction with LiAlH(4) gives the secondary phosphanes (Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))PH (5) and (Me(3)Si)(2)CH}(2-C(5)H(4)N)PH (6) in good yields as colourless oils. Metalation of 5 with Bu(n)Li in THF gives the lithium phosphanide [[(Me(3)Si)(2)CH}(C(6)
(Me(3)Si)(2)CH} PC1(2)(4)与一当量的[C(6)H(4)-2-NMe(2)] Li或[2- C(5)H(4)N] ZnCl,然后用LiAlH(4)原位还原得到仲膦(Me(3)Si)(2)CH}(C(6)H(4)-2 -NMe(2))PH(5)和(Me(3)Si)(2)CH}(2-C(5)H(4)N)PH(6),无色油的收率高。在THF中用Bu(n)Li对5进行金属化得到磷化锂[[(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))P] Li (THF)(2)](7),然后与NaOBu(t)或KOBu(t)进行复分解,得到较重的碱金属衍生物[[(Me(3)Si)(2)CH}(C( 6)H(4)-2-NMe(2))P] Na(tmeda)](8)和[[Me(3)Si)(2)CH}(C(6)H(4)- (9)在相应的胺共配体[tmeda = N