Synthesis and structural characterization of a tetramolybdate, (Mo sub 4 O sub 12 (C sub 8 H sub 6 N sub 4 )) sup 2 minus , containing a bridging phthalazine-1-hydrazido(2-) ligand. Comparison to the structure of (Mo sub 4 O sub 10 (OMe) sub 2 (NNMePh) sub 2 ) sup 2 minus , a tetramolybdate species exhibiting ligation to a terminal monodentate hydrazido(2-) group

Journal Article · Wed Jun 01 04:00:00 EDT 1988 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00284a017· OSTI ID:5208176

Shaikh, S N; Zubieta, J ^[1]

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1. State Univ. of New York, Albany (USA)

The reaction of (n-Bu{sub 4}N){sub 2}(Mo{sub 2}O{sub 7}) with 1-methyl-1-phenylhydrazine in CH{sub 2}Cl{sub 2}-methanol yields the tetranuclear poly oxomolybdate (n-Bu{sub 4}N){sub 2}(Mo{sub 4}O{sub 10}(OCH{sub 3}){sub 2}(NNMePh){sub 2}) (I). Complex I displays the methoxy-bridged binuclear core (MoO(NNMePh)({mu}-OCH{sub 3}){sub 2}MoO(NNMePh)){sup 2+}, bridged by two double-bridging bidentate (MoO{sub 4}){sup 2{minus}} units. Complex I is structurally related to the class of tetranuclear poly oxomolybdates coordinated to small organic molecules, (Mo{sub 4}O{sub 6-10}L{sub 1}L{sub 2}){sup n-}. The reaction of (n-Bu{sub 4}N){sub 2}(Mo{sub 2}O{sub 7}) with the potentially chelating and bridging hydrazino ligand hydrazinophthalazine, H{sub 2}NNH(C{sub 8}H{sub 5}N{sub 2}) (H{sub 2}-NNH-pht), yields the analogous tetranuclear species (n-Bu{sub 4}N){sub 2}(Mo{sub 4}O{sub 12}(HNN-pht))(II). Although structurally related to I, II reveals a number of distinctive features. The binuclear core (Mo{sub 2}O{sub 4}HNN-pht){sup 2+} displays a bridging oxo group and a bidentate bridging phthalazine moiety, in contrast to the two bridging methoxy groups of I. The Mo centers of this core are nonequivalent, one exhibiting MoO{sub 4}N{sub 2} coordination and the other (MoO{sub 5}N). The bridging (MoO{sub 4}){sup 2{minus}} moieties display unexceptional geometry. The {sup 17}O NMR spectra of I, II, and the related 1,4-dihydrazinophthalazine derivative (Mo{sub 4}O{sub 11}(C{sub 8}H{sub 6}N{sub 6})){sup 2{minus}} are consistent with the solid-state structures, exhibiting resonances in the regions assigned to doubly bridging Mo{sub 2}O groups (350-450 ppm) and to terminal MoO groups (750-950 ppm). Crystal data for the complexes are reported. 28 references, 3 figures, 7 tables.

• OSTI ID: 5208176
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 27:11; ISSN 0020-1669; 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
ALKANES
AROMATICS
CRYSTAL STRUCTURE
DATA
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
ISOTOPES
LIGHT NUCLEI
MOLECULAR STRUCTURE
MOLYBDENUM COMPOUNDS
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN 17
OXYGEN ISOTOPES
REFRACTORY METAL COMPOUNDS
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS