Synthesis and characterization of rectangular tetranuclear cluster complexes of molybdenum(II) by condensation of quadruply bonded dimers

Journal Article · Sat May 01 04:00:00 EDT 1982 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00135a069· OSTI ID:5262099

Ryan, T R; McCarley, R E

Several new synthetic methods have been developed for preparation of the rectangular tetrameric cluster complexes Mo/sub 4/X/sub 8/L/sub 4/ (X = Cl, Br, I; L = neutral donor ligand). Mo/sub 4/Cl/sub 8/(CH/sub 3/OH)/sub 4/ is prepared efficiently from the dimer Mo/sub 2/Cl/sub 4/(PPh/sub 3/)/sub 2/(CH/sub 3/OH)/sub 2/ and subsequently converted in good yield to Mo/sub 4/Cl/sub 8/(C/sub 2/H/sub 5/CN)/sub 4/ by reaction with propionitrile. Reaction of Mo/sub 4/Cl/sub 8/(C/sub 2/H/sub 5/CN)/sub 4/ with triphenylphosphine yields Mo/sub 4/Cl/sub 8/(PPh/sub 3/)/sub 4/, and with tetrahydrofuran the unstable Mo/sub 4/Cl/sub 8/(THF)/sub 4/ is afforded. The trialkylphosphine derivatives Mo/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/ (R = C/sub 2/H/sub 5/ or C/sub 4/H/sub 9/) may be obtained more conveniently in reactions between (a) K/sub 4/Mo/sub 2/Cl/sub 8/ + PR/sub 3/ (1:2 mole ratio), (b) Mo/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/ + PR/sub 3/ + (CH/sub 3/)/sub 3/SiCl (1:2:4 mole ratio), (c) Mo/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/ + PR/sub 3/ + AlCl/sub 3/ (1:2:2 mole ratio), or (d) Mo/sub 2/Cl/sub 4/(PR/sub 3/)/sub 4/ + Mo(CO)/sub 6/ (1:1 mole ratio). The Mo/sub 4/Br/sub 8/(P-n-Bu/sub 3/)/sub 4/ prepared by analogous methods exhibits properties closely related to the chloride derivative; Mo/sub 4/I/sub 8/(P-n-Bu/sub 3/)/sub 4/ however appears to consist of weakly coupled quadruply bonded dimers. The various compounds have been characterized by UV-visible, infrared, and Cl 2p photoelectron spectra which reflect the basic rectangular cluster structure known for Mo/sub 4/Cl/sub 8/(PEt/sub 3/)/sub 4/.

• Research Organization: Ames Lab., IA
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5262099
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 21:5; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ABSORPTION SPECTRA
BINDING ENERGY
COMPLEXES
DATA
DIMERS
ELECTRON SPECTROSCOPY
ENERGY
EXPERIMENTAL DATA
INFORMATION
INFRARED SPECTRA
LIGANDS
MOLYBDENUM COMPLEXES
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
SPECTRA
SPECTROSCOPY
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA