Molybdenum complexes of 1,2-bis(diphenylphosphino)benzene. Mononuclear molybdenum(II) species formed by facile metal-metal bond cleavage of the (Mo-/sup 4/Mo)/sup 4+/ core

Journal Article · Wed Jul 27 00:00:00 EDT 1988 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00288a011· OSTI ID:5833138

Bakir, M; Cotton, F A; Cudahy, M M; Simpson, C Q; Smith, T J; Vogel, E F; Walton, R A

The quadruply bonded dimolybdenum(II) complexes K/sub 4/Mo/sub 2/Cl/sub 8/, (NH/sub 4/)/sub 5/MoCl/sub 9/ /times/ H/sub 2/O, and (NH/sub 4/)/sub 4/Mo/sub 2/Br/sub 8/ react with 1,2-C/sub 6/H/sub 4/(PPh/sub 2/)/sub 2/(dppbe) in methanol at room temperature to afford /alpha/-Mo/sub 2/X/sub 4/(dppbe)/sub 2/ complexes (X = Cl, Br), which do not isomerize to the /beta/ isomers. Under more forcing reactions conditions (refluxing 1-propanol), these same reactions give mononuclear trans-MoX/sub 2/(dppbe)/sub 2/ in good yield (ca. 50%) together with some (MoOX(dppbe)/sub 2/)X /times/ nH/sub 2/O. An alternative synthetic strategy for the preparation of /alpha/-Mo/sub 2/X/sub 4/(dppbe)/sub 2/ involves the reaction of Mo/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/ with dppbe and Me/sub 3/SiX in THF. The compound MoCl/sub 2/(dppbe)/sub 2/ forms crystals in space group P2/sub 1//n, with the following unit cell parameters: a = 10.884 (2) /angstrom/, b = 12.753 (2) /angstrom/, c = 18.141 (4) /angstrom/, /beta/ = 91.43 (2)/degree/, V = 2517 (2) /angstrom//sup 3/, and Z = 2. The centrosymmetric trans molecule has Mo-Cl = 2.410 (1) /angstrom/, Mo-P = 2.481 (1), 2.511 (1) /angstrom/, and P-Mo-P(intra-ring) = 78.68 (4)/degree/. 25 refs., 1 fig., 4 tabs.

• Research Organization: Purdue Univ., West Lafayette, IN (USA)
• OSTI ID: 5833138
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:15; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
AROMATICS
BARYONS
CHEMICAL BONDS
COMPLEXES
DATA
ELEMENTARY PARTICLES
EXPERIMENTAL DATA
FERMIONS
HADRONS
INFORMATION
ISOTOPES
LIGHT NUCLEI
MOLYBDENUM COMPLEXES
NMR SPECTRA
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
PROTONS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES