SPECTROSCOPIC STUDIES OF A SQUARE-PYRAMIDAL NITRIDOCHROMIUM(V) COMPLEX

被引：25
作者：
AZUMA, N [1 ]
OZAWA, T [1 ]
TSUBOYAMA, S [1 ]
机构：
[1] INST PHYS & CHEM RES,WAKO,SAITAMA 35101,JAPAN
来源：
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1994年 / 18期
关键词：
D O I：
10.1039/dt9940002609
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The ESR and UV/VIS spectra have been studied for solutions of [N,N'-bis(pyridine-2-carbonyl)-o-phenylenediamido] nitridochromium(V) having a square-pyramidal (CrN5) chromophore. The g and Cr-53 hyperfine coupling tensors (A) are axially symmetric. An analysis of the A tensor indicated a 3d(xy) ground-state Kramers doublet. Fairly high d(pi)-p(pi) interaction in the Cr=N formally triple bond was also revealed. The striking stability of this complex can be attributed to the remarkable d(pi)-p(pi) covalency of the Cr=N bond. None of the d-d* transitions has been observed in the region of lambda greater than or equal to 600 nm at room temperature. Bands at 25000 and 29000 cm(-1) have been tentatively assigned to charge-transfer transitions. The considerable difference between the A(perpendicular to)(Cr-53), a(Cr-53), g(perpendicular to) and g(iso) values of nitrido-and those of oxo-chromium(V) complexes have been explained in terms of the different extents of covalency in the Cr=N and Cr=O multiple bonds.
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页码：2609 / 2613
页数：5
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