TY - JOUR
T1 - Electronic and molecular structure of [Cr(N)(NCO)4]2-, the first example of a mixed nitride-cyanate complex
AU - Brock-Nannestad, Theis
AU - Hammershøi, Anders
AU - Schau-Magnussen, Magnus
AU - Vibenholt, Johan Elias
AU - Bendix, Jesper
PY - 2011/1
Y1 - 2011/1
N2 - Metathesis of [Cr(N)Cl4]2- with excess cyanate affords the title complex which is the first example of a nitride complex with only cyanate auxiliary ligands. The electronic spectrum allows assignment of the ligand field transitions: B1(C4v) B2(C 4v) and E(C4v) B2(C4v). From these data, cyanate can be deduced to be intermediate between azide and thiocyanate with respect to σ-donation and comparable to thiocyanate, but weaker than azide with respect to π-donation. Solution EPR demonstrates the cyanate ligands to be N-bonded with similar super-hyperfine couplings to all nitrogen ligators, and the X-ray crystal structure of (Ph3PNPPh 3)2[Cr(N)(NCO)4] (1) establishes the expected 5-coordinate square pyramidal structure with a short Cr-N(nitride) bond, 1.520(5) Å and chromium-cyanate bond lengths in the range 1.948(12)-2.05(2) Å.
AB - Metathesis of [Cr(N)Cl4]2- with excess cyanate affords the title complex which is the first example of a nitride complex with only cyanate auxiliary ligands. The electronic spectrum allows assignment of the ligand field transitions: B1(C4v) B2(C 4v) and E(C4v) B2(C4v). From these data, cyanate can be deduced to be intermediate between azide and thiocyanate with respect to σ-donation and comparable to thiocyanate, but weaker than azide with respect to π-donation. Solution EPR demonstrates the cyanate ligands to be N-bonded with similar super-hyperfine couplings to all nitrogen ligators, and the X-ray crystal structure of (Ph3PNPPh 3)2[Cr(N)(NCO)4] (1) establishes the expected 5-coordinate square pyramidal structure with a short Cr-N(nitride) bond, 1.520(5) Å and chromium-cyanate bond lengths in the range 1.948(12)-2.05(2) Å.
U2 - 10.106/j.inoche.2010.11.005
DO - 10.106/j.inoche.2010.11.005
M3 - Journal article
SN - 1387-7003
VL - 14
SP - 251
EP - 253
JO - Inorganic Chemistry Communications
JF - Inorganic Chemistry Communications
ER -