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Article: Experimental and theoretical density studies on a nitrido-chromium(V) complex [CrV(bpb)N]

TitleExperimental and theoretical density studies on a nitrido-chromium(V) complex [CrV(bpb)N]
Authors
Issue Date1995
Citation
Journal Of Physical Chemistry, 1995, v. 99 n. 38, p. 13899-13908 How to Cite?
AbstractThis work gives the first example of a combined experimental and theoretical electron density study of a M-Nnitrido triple bond. The electron density distribution of a chromium(V)-nitrido complex, CrV(bpb)N (bpb2- = 1,2-bis(2-pyridinecarboxamido)benzene), was investigated both by single-crystal X-ray diffraction measurement at 120 K and by molecular orbital calculations. The compound belongs to the space F21, Z = 2, Mr = 382.32, a = 5.977(1) Å, b = 13.208(2) Å, c = 9.776(1) Å, β = 90.27(1)°, V = 771.7(2) Å3, Mo Kα radiation (λ = 0.7107 Å, μ = 0.75 mm-1), Rf = 4.1%, and Rw = 2.5% for 5975 observed reflections. Cr is five-coordinated in a square pyramidal fashion. There are three different Cr-N bonds in this compound, namely, Cr-Nnitrido, Cr-Namido, and Cr-Npyridine bonds. Deformation density maps were derived from the multipole model and from the theoretically calculated ones based on ab initio and DFT (density functional theory) calculations. The accumulation of deformation density along the C-H, C-C, C-N, and C-O bonds in the bpb ligand is clearly demonstrated for their covalent character. The agreement between the density maps obtained from the multipole model and from molecular orbital calculations is excellent in the ligand part. Some discrepancies are found near the Cr nucleus. Net atomic charges from multipole refinement are in reasonable agreement with those derived from ab initio calculations and the DFT method. Analysis of natural bonding orbitals (NBOs) reveals that the Cr-Nnitrido has a triple-bond character (σ2π4) and the four N of bpb behave as σ-donors to Cr with Cr-Namido a polarized covalent bond and Cr-Npyridine an essentially dative bond. d-orbital populations of Cr are derived by both experiment and theory; they are in good agreement with each other. An unpaired electron is found on the nonbonding d-orbital of the Cr atom. © 1995 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167325
ISSN
1998 Impact Factor: 4.173
1999 SCImago Journal Rankings: 1.721
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorWang, CCen_US
dc.contributor.authorWang, Yen_US
dc.contributor.authorChou, LKen_US
dc.contributor.authorChe, CMen_US
dc.date.accessioned2012-10-08T03:05:40Z-
dc.date.available2012-10-08T03:05:40Z-
dc.date.issued1995en_US
dc.identifier.citationJournal Of Physical Chemistry, 1995, v. 99 n. 38, p. 13899-13908en_US
dc.identifier.issn0022-3654en_US
dc.identifier.urihttp://hdl.handle.net/10722/167325-
dc.description.abstractThis work gives the first example of a combined experimental and theoretical electron density study of a M-Nnitrido triple bond. The electron density distribution of a chromium(V)-nitrido complex, CrV(bpb)N (bpb2- = 1,2-bis(2-pyridinecarboxamido)benzene), was investigated both by single-crystal X-ray diffraction measurement at 120 K and by molecular orbital calculations. The compound belongs to the space F21, Z = 2, Mr = 382.32, a = 5.977(1) Å, b = 13.208(2) Å, c = 9.776(1) Å, β = 90.27(1)°, V = 771.7(2) Å3, Mo Kα radiation (λ = 0.7107 Å, μ = 0.75 mm-1), Rf = 4.1%, and Rw = 2.5% for 5975 observed reflections. Cr is five-coordinated in a square pyramidal fashion. There are three different Cr-N bonds in this compound, namely, Cr-Nnitrido, Cr-Namido, and Cr-Npyridine bonds. Deformation density maps were derived from the multipole model and from the theoretically calculated ones based on ab initio and DFT (density functional theory) calculations. The accumulation of deformation density along the C-H, C-C, C-N, and C-O bonds in the bpb ligand is clearly demonstrated for their covalent character. The agreement between the density maps obtained from the multipole model and from molecular orbital calculations is excellent in the ligand part. Some discrepancies are found near the Cr nucleus. Net atomic charges from multipole refinement are in reasonable agreement with those derived from ab initio calculations and the DFT method. Analysis of natural bonding orbitals (NBOs) reveals that the Cr-Nnitrido has a triple-bond character (σ2π4) and the four N of bpb behave as σ-donors to Cr with Cr-Namido a polarized covalent bond and Cr-Npyridine an essentially dative bond. d-orbital populations of Cr are derived by both experiment and theory; they are in good agreement with each other. An unpaired electron is found on the nonbonding d-orbital of the Cr atom. © 1995 American Chemical Society.en_US
dc.languageengen_US
dc.relation.ispartofJournal of Physical Chemistryen_US
dc.titleExperimental and theoretical density studies on a nitrido-chromium(V) complex [CrV(bpb)N]en_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/j100038a022-
dc.identifier.scopuseid_2-s2.0-0001190769en_US
dc.identifier.volume99en_US
dc.identifier.issue38en_US
dc.identifier.spage13899en_US
dc.identifier.epage13908en_US
dc.identifier.isiWOS:A1995RW49900022-
dc.identifier.scopusauthoridWang, CC=35202304900en_US
dc.identifier.scopusauthoridWang, Y=36072665800en_US
dc.identifier.scopusauthoridChou, LK=36924248900en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US

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