Crystal Structure, Reactivity, and Photochemical Properties of Tungsten(0) Zwitterionic Amido Complex (CO)5 WNPhNPhC(OMe)Ph.

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Abstract:

The crystal structure of the zwitterionic complex CO5WNPhNPhCPhOMe 1 shows that it is best described as an amido complex in which the imidate fragment PhNCPhOMe serves as a substituent on the amide nitrogen. The structural information allows the previously reported conversion of 1 to an isomeric zwitterion to be assigned as simple rotation about the N-C double bond. The twisted intermediate for such a rotation also offers a pathway for the previously reported isomerization of 1 to a 2,4-diazametallacycle. The electronic spectrum of 1 reveals a low energy MLCT transition that is responsible for its photodecomposition via N-N bond cleavage. INDO1 CI calculations support assignment of the MLCT band as the HOMO to LUMO transition, where depopulation of the HOMO initiates the cleavage of the N-N bond.

Author(s):
Massey, Scott T. ; Barnett, Nicholas D. ; Abboud, Khalil A. ; Mcelwee-white, Lisa
Author Organization(s):
FLORIDA UNIV GAINESVILLE DEPT OF CHEMISTRY
Descriptive Note:
Technical rept.,
Pagination:
0032

Security Markings

DOCUMENT & CONTEXTUAL SUMMARY

Distribution:
Approved For Public Release, Document Partially Illegible
Distribution Statement:
Availability: Document Partially Illegible.

RECORD

Collection: TR
Identifying Numbers
Report Number(s):
TR-7
Contract/Grant Number(s):
N00014-95-1-0563
Monitor Series:
ONR
 Subject Terms
Joint Capability Areas:
JCA_6.3.3_Spectrum Management; JCA_6_Net Centric; JCA_6.3_Net Management; JCA_3.2_Engagement; JCA_3_Force Application; JCA_3.2.1_Kinetic Means; JCA_1.2_Force Preparation; JCA_1_Force Support; JCA_1.2.3_Educating; JCA_1.2.7_Experimentation; JCA_5_Command and Control; JCA_5.3_Planning
Communities of Interest:
Energy and Power Technologies
Descriptor(s):
*CRYSTAL STRUCTURE, *PHOTOCHEMICAL REACTIONS, *CHEMICAL PROPERTIES, *REACTIVITIES, *NITROGEN, *AMIDES, *TUNGSTEN, METALS, COMPUTATIONS, METHYL RADICALS, STRUCTURAL PROPERTIES, CHEMICAL BONDS, ELECTRONS, LOW ENERGY, LIGANDS, CHARGE TRANSFER, VALENCE, ROTATION, PHENYL RADICALS, CLEAVAGE, MOLECULAR ORBITALS, PHOTODECOMPOSITION
Field(s)/Group(s):
Inorganic Chemistry, Organic Chemistry, Physical Chemistry, Radiation and Nuclear Chemistry, Crystallography
Keyword(s):
*AMIDO COMPLEX, *ZWITTERIONIC COMPLEX, MLCT(METAL TO LIGAND CHARGE TRANSFER), DIAZAMETALLACYCLE, HOMO(HIGHEST OCCUPIED MOLECULAR ORBIT), INDO(INTERMEDIATE NEGLECT OF DIFFERENTIAL OVERLAP), CI(CONFIGURATION INTERACTION), HIGHEST OCCUPIED MOLECULAR ORBIT, INTERMEDIATE NEGLECT OF DIFFERENTIAL OVERLAP
Report Date:
1996 May 01
Creation Date:
1996 Jun 25