479620-99-0Relevant articles and documents
Six-coordinate molybdenum nitrosyls with a single ene-1,2-dithiolate ligand
Joshi, Hemant K,Inscore, Frank E,Schirlin, Julien T,Dhawan, Ish K,Carducci, Michael D,Bill, Tonja G,Enemark, John H
, p. 275 - 286 (2002)
The synthesis and molecular structures of the (Tp*)Mo(NO)(S-S) family of compounds (where (Tp*) is hydrotris(3,5-dimethyl-1-pyrazolyl)borate; (S-S) is an ene-1,2-dithiolate) are reported. The compounds; (Tp*)Mo(NO)(bdt) (1), (Tp*)Mo(NO)(tdt) (2), and (Tp*)Mo(NO)(bdtCl2) (3) (bdt, 1,2-benzenedithiolate; tdt, 3,4-toluenedithiolate; bdtCl2, 3,6-dichlorobenzenedithiolate), are the first such structurally characterized {MoNO}4 compounds that contain a [(Tp*)Mo(NO)]2+ fragment ligated to an ene-1,2-dithiolate. The compounds crystallize in the space groups P21/c (1) (a=11.115(2) ?, b=13.667(3) ?, c=16.410(3) ?; β=98.36(3), Volume=2466.4(8) ?3, Z=4); P21/n (2) (a=15.579(3) ?, b=9.942(2) ?, c=16.527(3) ?; β=95.79(3), Volume=2546.7(9) ?3, Z=4); and Pnma (3) (a=17.9879(9) ?, b=13.2277(7) ?, c=11.2505(6) ?; Volume=2676.9(2) ?3, Z=4). The molecular structures show that the inner coordination sphere remains invariant within this family. A remarkable feature is the fold angle (0) between the MoS2 plane and S2C2 plane of the ene-1, 2-dithiolate chelate ring. The fold angles (0) of 42.1 in 1, 41.1 in 2 and 44.4 in 3 are substantially larger than in analogous compounds with a terminal oxo group. Additional insight into the chemistry and properties of complexes 1-3 has been obtained by cyclic voltammetry, IR, NMR, electronic absorption and He I photoelectron (PES) spectroscopies.
