Accession Number : ADA309126

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

Descriptive Note : Technical rept.,

Corporate Author : FLORIDA UNIV GAINESVILLE DEPT OF CHEMISTRY

Personal Author(s) : Massey, Scott T. ; Barnett, Nicholas D. ; Abboud, Khalil A. ; McElwee-White, Lisa

PDF Url : ADA309126

Report Date : MAY 1996

Pagination or Media Count : 32

Abstract : The crystal structure of the zwitterionic complex (CO)5WNPhNPhC(Ph)OMe (1) shows that it is best described as an amido complex in which the 'imidate' fragment PhN=C(Ph)OMe 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. INDO/1 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.

Descriptors :   *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.

Subject Categories : Inorganic Chemistry
      Organic Chemistry
      Physical Chemistry
      Radiation and Nuclear Chemistry
      Crystallography

Distribution Statement : APPROVED FOR PUBLIC RELEASE