Preparation and characterisation of mononuclear organoimido complexes of tungsten: X-ray crystal structures of [WCl4(NC6H4Me-p)(thf)], [P(CH2Ph)Ph3][WCl5(NC6H4Me-p)], and [WCl2(NPh)2(bipy)]

Abstract

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)".

Homogeneous Decomposition of Aryl- and Alkylimido Precursors for the Chemical Vapor Deposition of Tungsten Nitride: A Combined Density Functional Theory and Experimental Study

“…Their N−W−Cl bond angles are greater than the ideal 90°, as expected for an octahedral complex with a single multiply bonded ligand . The W−N bond lengths and the bond angles about the tungsten center are in reasonable accord with experimental values obtained for related complexes by X-ray diffraction ,, and standard literature values . Minor differences in bond lengths and angles can be attributed, at least in part, to crystal packing forces that are not present in gas-phase calculations.…”

Tungsten Allylimido Complexes Cl4(RCN)W(NC3H5) as Single-Source CVD Precursors for WNxCy Thin Films. Correlation of Precursor Fragmentation to Film Properties

“…The results of single-crystal structure determination of complex 3a appear in Figure and Tables and . As has been previously reported for analogous tungsten imido complexes, , the overall geometry at the tungsten center is octahedral with the imido and acetonitrile ligands located in a trans orientation with respect to each other. The alkene carbons of the allyl moiety are disordered, and for brevity, only one set of positions [C(2)‘ and C(3)‘] will be discussed.…”

Synthesis of (tBu3SiNH)2ClW⋮WCl(NHSitBu3)2 and Its Degradation via NH Bond Activation

“…Structure of ( t Bu 3 SiN) 2 WCl 2 (py) (6-py). Confirmation of the pseudo-tbp structure of ( t Bu 3 SiN) 2 WCl 2 (py) ( 6 -py) was obtained via a single-crystal X-ray structure determination (Table , Table , Figure ). Crystallographically equivalent, bulky t Bu 3 SiN groups ( d (WN) = 1.747(5) Å; ∠ N1−W−N1A = 110.8(4)°) and the pyridine occupy equatorial positions ( d (WN) = 2.275(7) Å; ∠ N1−W−N2 = 124.6(2)°).…”