Some mononuclear organoimido complexes of Wv' and W have been prepared and the X-ray structures of [WCl,( NC,H,Me-p) (thf)] (thf = tetrahydrofuran) (1) and [P(CH,Ph) PhJ -[WCI,(NC,H,Me-p)](2) determined. In both species the octahedral Wv' centre is strongly bound to the tolylimido group [W=N 1.71 1 (7) for (1) and 1.709( 11) 8( for (Z)] causing a bending down of the four equatorial W-CI bonds [W-CI 2.31 3(4)-2.349( 6) A] and a lengthening of the trans bond [W-0 2.237(6), W-CI 2.464( 5) A]. The 14N and '*N n.m.r. spectra of the ethylimido compounds [WCI,( NEt) (thf)] and [P( CH,Ph) PhJ [WCIJ NEt)], and the t-butylimido compound [W( NBut),( NHBut),] have been obtained. From reactions of the binuclear bis(organoimid0) complexes [{WCI,( N R) (NR') (NH,R' )),] with neutral ligands [ PMe, or 2,2'-bipyridyl (bipy)] the mononuclear bis(organoimido) complexes [WCI,( NR) (NR') (PMe,),]and [WCI,( NR) (NR') (bipy)] were obtained. The X-ray crystal structure of [WCl,( NPh),( bipy)] has been determined and the distorted octahedral structure comprises cis-phenylimido groups and trans-dichloro ligands with the bipy nitrogens trans to the imido nitrogens. The phenylimido ligands are equivalent with mean W=N bond lengths of 1.775( 14) and 1.782( 14) 8( and mean W-N-C angles of 165.3(12) and 166.3( 12)".
274ChemInform Abstract The reaction of the phenylimido-bridged W(VI) complex (I) with an excess of the silylamine (II) or with the amine (III) yields the first title complex (IVa). The analogue (IVb)-(IVe), (V) and isomeric mixtures of (VI) are obtained from corresponding dimeric imidotetrachloro-W compounds and silylamines. Molecular and crystal structures of the title complexes (IVa) (space group P21/n, Z=2) and (IVb) (P1, Z=1) are determined. The tert.butylamine ligands are involved in intramolecular NH...Cl bridging within the dimeric unit. IR, 1H and 13C NMR data are tabulated and discussed in terms of the bridging and terminal ligands in the dimers. Spectral studies suggest that these complexes arise from two cis-oriented organoimido groups by an inter-ligand proton-transfer process which proceeds regardless of the size of the substituent R2 (no further yields given).
Bis-organoimido complexes of tungsten(vi) are prepared by reaction of WCI6 with Me3SiNHCMe3, or by reaction of mono-organoimido complexes with the silylamines Me3SiNHR; the structure of [WC12(NPh)2(bipy)] (bipy = a,a-bipyridyl) has been established by X-ray crystallography.
275ChemInform Abstract The mononuclear organoimido-W(VI) complexes (I)-(IV) are prepared according to the scheme and characterized by spectroscopic (IR, 1H, 13C NMR) data as well as by X-ray structure analysis of the title complexes (Ia) (space group P21/n, Z=4), (IIa) (P21/a, Z=4), and (IIIa) (P1, Z=4). Correspondingly, the imido-W(V) complexes (XII) are obtained starting with (WCl4(NPh))2 (for (XII) yields givenin g).
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