Structural Characterization and Coordination Behavior of 1,2-Diphosphino and 1,2-Diarsino-Diborane(4) Compounds

Article type: Research Article

Authors: Moezzi, Afarin | Olmstead, Marilyn M. | Pestana, Doris C. | Ruhlandt-Senge, Karin | Power, Philip P.

Affiliations: Department of Chemistry, University of California, Davis, California 95616

Note: [] Corresponding author

Abstract: Reaction of either LiPPh2 or LiAsMes2 with the diborane(4) compound (Me2N) BrBBBr (NMe2) affords the compounds (Me2N) (Ph2P)BB(PPh2) (NMe2), 1, and (Me2N) (Mes2As)BB(AsMes2)(NMe2)·0.5 PhMe, 2·0.5PhMe (Mes = 2,4,6-Me3C6H2-). Both 1 and 2 feature normal B–B single bond lengths; however, the empty boron p-orbitals display strong π-interactions with the dimethylamino substituents. The B–P and B–As distances and the pyramidal phosphorus and arsenic geometries are consistent with single bonding. Furthermore, the stereochemical activity of the phosphorus and arsenic lone pairs is demonstrated by the ready formation of the complex cis-[Cr(CO)4(Me2N) (Ph2P)BB(PPh2)(NMe2)]·C6H6, 3·C6H6, by treatment of 1 with [Cr(CO)4(2,5-norbornadiene)]. Compounds 1–3 were characterized by X-ray crystallography, 11B and 31P NMR spectroscopy, and by IR spectroscopy in the case of 3.

DOI: 10.1080/13583149612331338435

Journal: Main Group Chemistry, vol. 1, no. 2, pp. 197-206, 1996