Bonding in tris(. eta. sup 5 -cyclopentadienyl) actinide complexes. 5. A comparison of the bonding in Np, Pu, and transplutonium compounds with that in lanthanide compounds and a transition-metal analogue

Journal Article · Tue Jan 15 23:00:00 EST 1991 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00002a024· OSTI ID:5289702

Strittmatter, R J; Bursten, B E ^[1]

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1. Ohio State Univ., Columbus (USA)

Cp{sub 3}An (An = U, Np, Pu, Am, Cm, Bk, Cf) compounds have been investigated via X{alpha}-SW molecular orbital calculations with quasi-relativistic corrections. The 5f-orbital energy drops across the series while the 6d-orbital energy rises. Due to the greater radial extension of the 6d orbitals, the metal 6d orbitals are more important in bonding the Cp ligands than the 5f orbitals. Comparison of the actinide compounds with the lanthanide series reveals some minor differences. The 4f orbitals and 6s orbital of the lanthanides are not as effective at bonding the Cp ligands as the 5f orbitals and 7s orbital of the actinides. Also, the semicore 5p orbitals of the lanthanides have a greater antibonding influence on the Cp ligands than do the 6p orbitals of the actinides. Comparison of the actinide compounds with ({eta}{sup 5}-Cp){sub 3}Zr shows some major differences. The 4d orbitals of zirconium are much more effective at bonding the Cp ligands than the 6d orbitals of the actinides.

• DOE Contract Number: FG02-86ER13529
• OSTI ID: 5289702
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 113:2; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTINIDE COMPOUNDS
ALKENES
AMERICIUM COMPOUNDS
BERKELIUM COMPOUNDS
CALIFORNIUM COMPOUNDS
CHEMICAL BONDS
CURIUM COMPOUNDS
CYCLOALKENES
CYCLOPENTADIENE
DATA
DIENES
HYDROCARBONS
INFORMATION
MEASURING METHODS
MOLECULAR ORBITAL METHOD
NEPTUNIUM COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
PLUTONIUM COMPOUNDS
POLYENES
THEORETICAL DATA
TRANSPLUTONIUM COMPOUNDS
TRANSURANIUM COMPOUNDS
URANIUM COMPOUNDS