Dimolybdenum(II) Bromide Complexes Containing Bidentate Tertiary Phosphine and Arsine Ligands: Kinetic vs. Thermodynamic Reaction Control and Structural Characterization of a Mononuclear Complex Resulting from M-M Bond Cleavage
Loading...
Authors
Derringer, Daniel R.
Issue Date
1984
Type
Thesis
Language
en_US
Keywords
Alternative Title
Abstract
The reactions of (NH4)4Mo2Br8 with bidentate tertiary
phosphine and arsine donors Ph2P(CH2)PPh2 (dppm), Ph2P(CH2)2PPh2
(dppe), Ph2P(CH2)2AsPh2 (arphos), Ph2P(CH2)3PPh2 (dppp) in
refluxing alcoholic solvents MeOH, EtOH and I-PrOH are described.
α and ß forms of the products with the general formula Mo2Br4(LL)2
are discussed. Low frequency infrared spectra (400 cm-I - 200 em-I)
and electronic absorption data suggest that Mo2Br4(dppm)2' ß-Mo2Br4
(dppe}2 and ß-Mo2Br4(dppp)2 are structurally similar to Mo2Br4(arphos)2
which has been shown to possess bridging arphos molecules. Available
evidence suggests that α-Mo2Br4(dppe)2 possesses chelating dppe molecules
and forms as the kinetic product which can be converted to the
thermodynamic ß-product in solutions of I-PrOH and deoxygenated dichloromethane.
Solvent dependence in reaction product distribution is
investigated, and the crystal structure of trans-MoBr2(dppe)2, a mononuclear
complex resulting from M-M bond cleavage, is reported.
Description
ix, 106 p.
Citation
Publisher
Kalamazoo College
License
U.S. copyright laws protect this material. Commercial use or distribution of this material is not permitted without prior written permission of the copyright holder. All rights reserved.