M. Westerhausen, M. Hartmann, W. Schwarz
Mar 3, 1998
Citations
0
Influential Citations
29
Citations
Journal
Inorganica Chimica Acta
Abstract
Abstract The reaction of yttrium tris [bis(trimethylilyl)methanide] (4) with bis (trimethylsilyl)phosphane in aromatic hydrocarbons yields dimeric yttrium tris [bis(trimethylsilyl)phosphanide] (5). The structure is deducted from NMR data. The quadruply coordinated phosphorus nuclei of the two bridging ligands show a triplet of quintets due to the coupling with both the yttrium and the four terminal bound phosphorus atoms, whereas the 31P(1H) resonance of the terminal phosphanide ligands split to doublets of triplets. The 1 J( 89 Y , 31 P ) coupling constants for the triply coordinated terminal phosphorus atoms are 122.4 Hz; for the μ-coordinated phosphorus atom a much smaller value of 56.7 Hz is observed. A synthesis of a yttrium tris(phosphanide) via the metathesis reaction of lithium di-tert-butylphosphanide and yttrium(III)chloride failed, only [(thf)2LiCl]2 (1) as well as [(thf)LiCl·(thf)2Li1PBu2]2 (2) were crystallized from a tetrahydrofuran solution. Crystallographic data for 2: monoclinic, P2 1 /n, a=963.3(2), b=1486.1(3), c=1760.7(4) pm , β=92.51(3)°, Z=2 dimers , wR 2 =0.1452; for 4 : hexagonal, P31c, a=b=1629.50(9), c=860.14(7), Z=2, wR2=0.1854.