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Dedictrtc~cl to Profixwr Hrrhert Roesky on I/IC o i w s i o n qf'hi,s 60th birthday,V-Silylated derivatives of 1.3-diazaallyl anions"' I are important chelate ligands for main group and transition metals['1 and have recently gained significance as cocatalysts for olefin polymerization.". 21 Compounds of the 1,3-diphosphaallyl system[31 (11) homologous to 1 are versatile complex ligdnds (a and TI coordination).lJ1 and activities in the olefin polymerization were detected for ;I nickel ~omplex.[~1 As an extension of our studies on 1 -phosphaallyl anions, ['] we became interested in the l-aza-3-phosphaallyl system"] (111) which combines the reactivity of 1 both due to the presence of a "soft" (phosphorus) and a "hard" reaction center (nitrogen). We report herein on a simple route to this heteroallyl system. the crystal structure of a lithium complex. and its reaction with electrophiles.The reaction of equimolar amounts of lithium phenyl phosphanide 1 a with acetonitrile in T H F leads smoothly to the lithium complex of the l-aza-3-phosphaallyl anion 2, which was i.s dimeric in the crystal (Fig. 1). The two heteroallyl anions are linked through a planar Li,N, unit; the lithium atoms attain a distorted tetrahedral geometry by the additional coordination of two T H F molecules. The Li-N distances lie in the expected rangel '"l (203.1(8). 209.0(8) pm). The acute Li-N-Li angle (75.6(4) ), which results in the two lithium atoms (253(2) pin) approaching one another, is particularly noteworthy. The coplanar arrangement of the atoms HI-Nl-Cl-C2-P1 -Cl1 (average deviation from the best plane: 0.5 pm) indicates the formation of a delocalized 4electron-3center-px system. This assumption is also supported by the short N1 -C1 and CI -PI distances (1 32.0(5) and 174.0(4) pm, respectively), which lie between those of a single and a double bond for these element

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