Octahedral d[sup 6] Bis(maleimide) and Bis(maleic anhydride) complexes of molybdenum

Journal Article · Wed Dec 08 00:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00077a003· OSTI ID:5037526

Lai, Chen-Hsing; Cheng, Chien-Hong; Liao, Fen-Ling; Wang, Sue-Lein ^[1]

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1. National Tsing Hua Univ., Taiwan (China)

Mo(CO)[sub 3](CH[sub 3]CN)[sub 3] reacts with 2 equiv of alkene, where the alkene is maleimide (MI), N-phenylmaleimide (PhMI), or N-methylmaleimide, to give the corresponding Mo(CO)[sub 2](alkene)[sub 2](CH[sub 3]CN)[sub 2] complex (1a-c, respectively) in excellent yield. Dissolution of 1 in DMSO led to the substitution of acetonitrile ligands by DMSO to form the corresponding cis bis(DMSO) complexes 2a-c. Addition of 1 equiv of NN to 1 yields MO(CO)[sub 2](alkene)[sub 2](alkene)[sub 2](NN) (NN = en, alkene = PhMI (3b), MeMI (3c); NN = o-phenylenediamine, alkene = PhMI (4)). Treatment of Mo-(CO)[sub 4](NN) (NN = phen or bpy), with 2 equiv of alkene in refluxed acetonitrile for 2 h gave Mo(CO)[sub 2]-(alkene)[sub 2](NN) (NN = phen, alkene = MI (5a), PhMI (5b); NN = bpy, alkene = MI (6a), PhMI (6b)). Treatment of Mo(CO)[sub 3](CH[sub 3]CN)[sub 3] with 2 equiv of maleic anhydride (MA) gave Mo(CO)[sub 2](MA)[sub 2](CH[sub 3]CN)[sub 2] (7). The acetonitrile ligands in 7 were replaced by DMSO molecules to give complex 8 as 7 was dissolved in DMSO. Similarly, the reaction of 7 with a bidentate ligand NN (phen or bpy) gave the substituted product Mo(CO)[sub 2](MA)[sub 2](NN) (9 or 10). The structures and conformations of 1b and 7 were determined by X-ray diffraction. Both molecules adopt an octahedral geometry with mutually perpendicular trans alkene ligands and each alkene ligand eclipses a N-Mo-CO vector. Each PhMI or MA is oriented so that the central nitrogen or oxygen atom points to a carbonyl group. 1b crystallizes in triclinic space group P1. There are three possible conformations for a trans bis(maleimide) or bis(maleic anhydride) complex (I-III). The results of X-ray and NMR studies indicated that the main conformation of complexes 1-10 is I both in the solid state and in solution.

• OSTI ID: 5037526
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:25; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
MOLYBDENUM COMPLEXES
MOLECULAR STRUCTURE
CARBONYLS
CHEMICAL REACTION YIELD
NUCLEAR MAGNETIC RESONANCE
ORGANOMETALLIC COMPOUNDS
TRICLINIC LATTICES
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
RESONANCE
TRANSITION ELEMENT COMPLEXES
YIELDS
400201* - Chemical & Physicochemical Properties