Nephelauxetic series of in-plane ligands for square-pyramidal nitridochromium(V) complexes as studied by means of ESR spectroscopy

Akiko Hori, Takehiro Ozawa, Hironobu Yoshida, Yohko Imori, Yoshihiko Kuribayashi, Emiko Nakano, Nagao Azuma

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

The crystal structure of the nitridochromium(V) complex [CrN(salophen)] · MeCN [H 2salophen=N,N′-bis(salicylidene)-o-phenylene-diamine] has been determined. The coordination geometry of this complex, similar to those of all the nitridochromium(V) complexes investigated so far, is square pyramidal with the nitride ion occupying the apex. The ESR parameters of the nitridochromium(V) complexes isolated so far were compared with one another to show an enormous expansion of the 3d electron cloud due to the strong Cr=N triple bonding. Moderate covalency in the in-plane bonds was also concluded. The nephelauxetic series of three types of the basal ligands is deduced to be salen≈salophen>bpb≈mebpb≈dmebpb>oep≈ttp (in nephlauxetic ratio) for the high-oxidation nitridochromium(V), H 2salen=N,N′-bis(salicylidene)ethane-1,2-diamine, H 2bpb=1,2-bis(pyridine-2-carboxamido)benzene, H 2mebpb=1,2-bis(pyridine-2-carboxamido)-4-methylbenzene, H 2dmbpb=1,2-bis(pyridine-2-carboxamido)-4,5-dimethylbenzene, H 2oep=2,3,7,8,12,13,17,18-octa-ethylporphyrin and H 2ttp=5,10,15,20-tetra-p-tolylporphyrin.

Original languageEnglish
Pages (from-to)207-213
Number of pages7
JournalInorganica Chimica Acta
Volume281
Issue number2
Publication statusPublished - 1998 Nov 1
Externally publishedYes

Fingerprint

Pyridine
Paramagnetic resonance
pyridines
ethylenediamine
Ligands
Spectroscopy
diamines
ligands
spectroscopy
Xylenes
electron clouds
Diamines
Coordination Complexes
Ethane
Benzene
Nitrides
ethane
nitrides
apexes
Crystal structure

Keywords

  • Chromium complexes
  • Crystal structures
  • Nitride complexes

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Nephelauxetic series of in-plane ligands for square-pyramidal nitridochromium(V) complexes as studied by means of ESR spectroscopy. / Hori, Akiko; Ozawa, Takehiro; Yoshida, Hironobu; Imori, Yohko; Kuribayashi, Yoshihiko; Nakano, Emiko; Azuma, Nagao.

In: Inorganica Chimica Acta, Vol. 281, No. 2, 01.11.1998, p. 207-213.

Research output: Contribution to journalArticle

Hori, A, Ozawa, T, Yoshida, H, Imori, Y, Kuribayashi, Y, Nakano, E & Azuma, N 1998, 'Nephelauxetic series of in-plane ligands for square-pyramidal nitridochromium(V) complexes as studied by means of ESR spectroscopy', Inorganica Chimica Acta, vol. 281, no. 2, pp. 207-213.
Hori, Akiko ; Ozawa, Takehiro ; Yoshida, Hironobu ; Imori, Yohko ; Kuribayashi, Yoshihiko ; Nakano, Emiko ; Azuma, Nagao. / Nephelauxetic series of in-plane ligands for square-pyramidal nitridochromium(V) complexes as studied by means of ESR spectroscopy. In: Inorganica Chimica Acta. 1998 ; Vol. 281, No. 2. pp. 207-213.
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AU - Imori, Yohko

AU - Kuribayashi, Yoshihiko

AU - Nakano, Emiko

AU - Azuma, Nagao

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AB - The crystal structure of the nitridochromium(V) complex [CrN(salophen)] · MeCN [H 2salophen=N,N′-bis(salicylidene)-o-phenylene-diamine] has been determined. The coordination geometry of this complex, similar to those of all the nitridochromium(V) complexes investigated so far, is square pyramidal with the nitride ion occupying the apex. The ESR parameters of the nitridochromium(V) complexes isolated so far were compared with one another to show an enormous expansion of the 3d electron cloud due to the strong Cr=N triple bonding. Moderate covalency in the in-plane bonds was also concluded. The nephelauxetic series of three types of the basal ligands is deduced to be salen≈salophen>bpb≈mebpb≈dmebpb>oep≈ttp (in nephlauxetic ratio) for the high-oxidation nitridochromium(V), H 2salen=N,N′-bis(salicylidene)ethane-1,2-diamine, H 2bpb=1,2-bis(pyridine-2-carboxamido)benzene, H 2mebpb=1,2-bis(pyridine-2-carboxamido)-4-methylbenzene, H 2dmbpb=1,2-bis(pyridine-2-carboxamido)-4,5-dimethylbenzene, H 2oep=2,3,7,8,12,13,17,18-octa-ethylporphyrin and H 2ttp=5,10,15,20-tetra-p-tolylporphyrin.

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