Preparation and characterization of binuclear complexes of molybdenum(III) and molybdenum(V) via oxidative decarbonylation. Reactions of LMo(CO)/sub 3/ (L = 1,5,9-triazacyclododecane) and crystal structure of anti-(L/sub 2/Mo/sub 2/O/sub 4/)(ClO/sub 4/)/sub 2/ x 2H/sub 2/O
The cyclic triamine 1,5,9-triazacyclododecane (L), C/sub 9/H/sub 21/N/sub 3/, reacts with Mo(CO)/sub 6/ in Decalin at 150/sup 0/ to yield yellow, air-stable LMo(CO)/sub 3/ (1). Oxidation of 1 with bromine, nitrous acid (or NOBF/sub 4/), or hydrochloric acid in the presence of O/sub 2/ affords the monomeric complexes (LMo(CO)/sub 3/Br)(Br/sub 3/), (LMo(CO)/sub 2/NO)BF/sub 4/, and LMoCl/sub 3/, respectively. Oxidative decarbonylation of 1 in HClO/sub 4/ with O/sub 2/ gives the two isomers purple anti-(L/sub 2/Mo/sub 2/O/sub 4/)/sub 2/(ClO/sub 4/)/sub 2/ x 2H/sub 2/O and yellow syn-(L/sub 2/Mo/sub 2/O/sub 4/)(ClO/sub 4/)/sub 2/ x H/sub 2/O. Reduction of the former with zinc amalgam in aqueous solution in the presence and absence of coordinating acids (HBF/sub 4/, formic acid, acetic acid, hydrochloric acid) affords diamagnetic, green, dimeric bis(..mu..-hydroxo)-bridged species of molybdenum(III): (L/sub 2/Mo/sub 2/(..mu..-OH)/sub 2/(OH)/sub 2/)I/sub 2/ x 2H/sub 2/O, (L/sub 2/Mo/sub 2/(..mu..-OH)/sub 2/(..mu..-HCOO))I/sub 3/ x 2H/sub 2/O, (L/sub 2/Mo/sub 2/(..mu..-OH)/sub 2/(..mu..-CH/sub 3/CO/sub 2/))I/sub 3/, and (L/sub 2/Mo/sub 2/(..mu..-OH)/sub 2/Cl/sub 2/)(ClO/sub 4/)/sub 2/. Purple anti-(L/sub 2/Mo/sub 2/O/sub 4/)(ClO/sub 4/)/sub 2/ x 2H/sub 2/O crystallizes in the monoclinic space group P2/sub 1//c with a = 8.515 (8) A, b = 11.11 (2) A, c = 16.56 (3) A, ..beta.. = 92.3 (1)/sup 0/, V = 1565 (1) A/sup 3/, and d/sub calcd/ = 1.77 g/cm/sup 3/ for Z = 2 and M/sub r/ = 833.4. Least-squares refinement of the structure based on 3216 observations led to final discrepancy indices of R = 0.039 and R/sub w/ = 0.045. 21 references, 4 figures, 6 tables.
- Research Organization:
- Ruhr-Universitaet, Bochum, West Germany
- OSTI ID:
- 5987698
- Journal Information:
- Inorg. Chem.; (United States), Vol. 24:20
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
MOLYBDENUM COMPLEXES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
OXIDATION
CARBONYLATION
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
ISOMERIZATION
COMPLEXES
DATA
INFORMATION
KINETICS
NUMERICAL DATA
REACTION KINETICS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
360102* - Metals & Alloys- Structure & Phase Studies
400201 - Chemical & Physicochemical Properties