| Popis: |
A new phosphaazaallene Mes*PCNAr (Mes*=2,4,6- t Bu 3 C 6 H 2 , Ar= p -ClC 6 H 4 ) ( 1 ) has been synthesized. Complex 1 reacts with Mes*PHSiMe 2 t Bu to form the phosphaazaallene insertion product Mes*PC(PHMes*)NAr(SiMe 2 t Bu) ( 2 ). The treatment of 1 with an excess amount of YCl 3 in THF leads to the isolation of the symmetrical dimer Mes*P(μ-CNAr) 2 PMes* ( 3 ), indicating both of the PC and CN bonds of 1 are reactive sites. X-ray structure analysis of 1 indicates that the distance of the PC bond, 1.642(5) A, is markedly shorter than those of isolated PC bonds (1.66–1.72 A), and the NCP unit slightly deviates from linearity with the PCN angle of 170.8(4)°. The structure determination of 2 revealed the molecule adopts a planar conformation about PC bond and the mutual orientation of two bulky Mes* moieties is almost orthogonal (92.8°). Complex 3 is a symmetrical four-membered ring structure in which the Mes* rings lie nearly perpendicular to the planes of the Ar ring and the P 2 C 2 ring (84.8 and 75.6°, respectively), while the Ar ring is almost parallel to the plane of the P 2 C 2 ring (25.2°). |
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