The crystal and molecular structures of two derivatives of Mo(VI) with substituted hydrazine ligands, oxo[diphenylhydrazido(2-)] [N,N′-dimethyl-N,N′-bis(mercaptoethyl)ethylenediamine]molybdenum(VI), [MoO(N2Ph2)L], and [bis((p-methoxyphenyl)diazenido)][N,N′-dimethyl-N,N′-bis(mercaptoethyl)ethylenediamine]molybdenum(VI), [Mo(N2C6H4OCH3)2L], are reported. [MoO(N2Ph2)L] crystallizes as red needles in space group P21/c with unit cell dimensions a = 13.248 (2) Å, b = 11.229 (2) Å, and c = 15.780 (2) Å and with β = 109.46 (1)° and Z = 4. The structure has been refined to R1 = 0.027 and R2 = 0.048 on the basis of 2784 independent reflections. The molecule is pseudooctahedral with the hydrazido(2-) group eis to the oxo ligand. [Mo(N2C6H4OCH3)2L] crystallizes in space group Cc with unit cell dimensions a = 22.557 (2) Å, b = 8.483 (3) Å, and c = 18.030 (2) Å and with β = 133.25 (1)° and Z = 4. The structure refined to values of R1 and R2 of 0.043 and 0.049, respectively, on the basis of 1505 independent reflections. The diazenido ligands are mutually cis and enjoy significant multiple-bond interaction with the molybdenum, as indicated by the short average Mo-N distance of 1.81 (2) Å. In both structures, the ligand L exhibits the sterically strained configuration associated with this tetradentate ligand. The electrochemistry of a series of complexes of the type [Mo(N2C6H4X)2L] is discussed and related to the geometry of the diazenido ligands.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry