In:
Canadian Journal of Chemistry, Canadian Science Publishing, Vol. 82, No. 2 ( 2004-02-01), p. 285-292
Kurzfassung:
The monomeric trinitrosyl complex, W(NO) 3 Cl 3 , can be prepared by the treatment of WCl 6 in CH 2 Cl 2 with NO gas, and its identity has been unambiguously confirmed by a single-crystal X-ray diffraction analysis. The complex crystallizes in the space group Pmn2 1 as a three-component twin (a = 10.4280(4) Å, b = 6.3289(2) Å, c = 5.6854(2) Å, Z = 2, R 1 = 0.065, wR 2 = 0.176). Its solid-state molecular structure consists of a tungsten centre bound to three chloride ligands and three linear nitrosyl ligands in a fac-octahedral stereochemistry. In addition, the structure contains a crystallographically imposed mirror plane. The two independent WN linkages are 1.88(2) and 1.92(1) Å long, while the two corresponding NO bond lengths are 1.13(2) and 1.16(2) Å. DFT calculations on fac-W(NO) 3 Cl 3 at the B3LYP/LANL2DZ level of theory afford optimized intramolecular metrical parameters that match the X-ray crystallographically determined bond lengths and bond angles quite well. In addition, they provide a rationale for the nearly linear W-N-O linkages extant in the complex. Solutions of fac-W(NO) 3 Cl 3 in CH 2 Cl 2 lose ClNO under ambient conditions and deposit the well-known [W(NO) 2 Cl 2 ] n polymer, and this conversion is fully reversible.Key words: nitrosyl, tungsten, structure, bonding.
Materialart:
Online-Ressource
ISSN:
0008-4042
,
1480-3291
Sprache:
Englisch
Verlag:
Canadian Science Publishing
Publikationsdatum:
2004
ZDB Id:
1482256-8
