Insertion of carbon monoxide into metal-nitrogen bonds. Synthesis, chemistry, structures, and structural dynamics of bis(pentamethylcyclopentadienyl) organoactinide dialkylamides and eta/sup 2/-carbamoyls

Journal Article · Wed May 06 04:00:00 EDT 1981 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00399a013· OSTI ID:6454344

Fagan, P J; Manriquez, J M; Vollmer, S H; Day, C S; Day, V W; Marks, T J

This paper reports the synthesis and characterization of chlorobis(pentamethylcyclopentadienyl)thorium and -uranium dialkylamides, M(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(NR/sub 2/)Cl (M = Th, U; R = CH/sub 3/, C/sub 2/H/sub 5/), and bis(dialkylamides), M(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(NR/sub 2/)/sub 2/ (M = Th, U, R = CH/sub 3/; M = U, R = C/sub 2/H/sub 5/). The amide compounds undergo facile migratory insertion of carbon monoxide to produce the corresponding eta/sup 2/-carbamoyl complexes M(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(eta/sup 2/-CONR/sub 2/)Cl, M(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(eta/sup 2/-CONR/sub 2/)NR/sub 2/, and M(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(eta/sup 2/-CONR/sub 2/)/sub 2/ which were characterized by a variety of chemical and physicochemical methods. The infrared spectra of these compounds exhibit unusually low C-O stretching frequencies (1490 to 1560 cm/sup -1/) for carbamoyl complexes, indicative of strong metal-oxygen bonding. The molecular structures of Th(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(eta/sup 2/-CON(C/sub 2/H/sub 5/)/sub 2/)Cl and U(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(eta/sub 2/-CON(CH/sub 3/)/sub 2/)/sub 2/ have been determined by single-crystal x-ray diffraction techniques. For the chloro complex, least-squares refinement led to a value for the conventional R index (on F) of 0.080 for 3156 independent reflections having 2theta/sub MoK..cap alpha../ < 55/sup 0/ and I > 3sigma(I), while for the bis(carbamoyl), least-squares refinement led to a conventional R (on F) of 0.036 for 3689 independent reflections having 2 theta/sub MoK..cap alpha../ < 55/sup 0/ and I > 3sigma(I). The M((CH/sub 3/)/sub 5/C/sub 5/)/sub 2/ fragments of both molecules are of the bent sandwich M(C/sub 5/H/sub 5/)/sub 2/X/sub 2/ configuration, with the carbamoyl ligands bound in a eta/sup 2/ fashion. In the bis(carbamoyl), the U-O distances are 2.370 (5) and 2.342 (7) A, the corresponding U-C distances 2.405 (8) and 2.402 (9) A, and the corresponding U-C-O angles 73.0 (4) and 71.8 (5)/sup 0/. The structural and spectral data evidence dative nitrogen lone-pair donation to the carbenoid carbamoyl carbon atom. 6 figures, 8 tables.

• Research Organization: Northwestern Univ., Evanston, IL
• OSTI ID: 6454344
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:9; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry &amp; Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
BINDING ENERGY
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMISTRY
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
ELEMENTS
ENERGY
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
INFORMATION
INFRARED SPECTRA
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NITROGEN
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RESONANCE
ROTATIONAL STATES
SCATTERING
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
THORIUM COMPLEXES
URANIUM COMPLEXES
X-RAY DIFFRACTION