Polyselenide chemistry of indium and thallium in dimethylformamide, acetonitrile, and water. Syntheses, structures, and properties of the new complexes [In[sub 2](Se[sub 4])[sub 4](Se[sub 5])][sup 4[minus]], [In[sub 2]Se[sub 2](Se[sub 4])[sub 2]][sup 2[minus]], [In[sub 3]Se[sub 3](Se[sub 4])[sub 3]][sup 3[minus]], and [Tl[sub 3]Se[sub 3](Se[sub 4])[sub 3]][sup 3[minus]]

Journal Article · Wed Apr 14 04:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00060a007· OSTI ID:6265833

Dhingra, S S; Kanatzidis, M G ^[1]

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1. Michigan State Univ., East Lansing (United States)

The reaction of InCl[sub 3] with Na[sub 2]Se[sub 5] in dimethylformamide (DMF) in the presence of Ph[sub 4]PCl gave (Ph[sub 4]P)[sub 4][In[sub 2](Se[sub 4])[sub 4](Se[sub 5])] (I) in 75% yield. Under the same conditions, InCl[sub 3] reacted with Na[sub 2]Se[sub 5] in the presence of Pr[sub 4]NBr or Et[sub 4]NBr and afforded (Pr[sub 4]N)[sub 4][In[sub 2](Se[sub 4])[sub 4](Se[sub 5])] (II) in 65% yield and (Et[sub 4]N)[sub 4][In[sub 2](Se[sub 4])[sub 4](Se[sub 5])] (III) in 72% yield, respectively. Single-crystal X-ray diffraction studies show that (I), (II), and (III) contain the same anion, [In[sub 2](Se[sub 4])[sub 4](Se[sub 5])][sup 4[minus]]. The anion consists of In[sup 3+] centers in trigonal bipyramidal coordination; each In atom is chelated by two bidentate Se[sub 4][sup 2[minus]] ligands forming a [In(Se[sub 4])[sub 2]][sup [minus]] unit. Two of these [In(Se[sub 4])[sub 2]][sup [minus]] units are bridged by an Se[sub 5][sup 2[minus]] chain forming a dimer. The hydrothermal reaction of InCl[sub 3] with Na[sub 2]Se[sub 4] in the presence of Pr[sub 4]NBr and water at 110[degrees]C for 3 days in an evacuated sealed Pyrex tube afforded deep red crystals of (Pr[sub 4]N)[sub 2][In[sub 2]Se[sub 2](Se[sub 4])[sub 2]] (IV), in 80% yield. Under the same conditions the reaction with [(Ph[sub 3]P)[sub 2]N]Cl yields [(Ph[sub 3]P)[sub 2]N][sub 2][In[sub 2]Se[sub 2](Se[sub 4])[sub 2]] (V) in 60% yield. Single-crystal X-ray diffraction studies show that (IV) and (V) contain the same binuclear anion [In[sub 2]Se[sub 2](Se[sub 4])[sub 2]][sup 2[minus]]. The reaction of InCl[sub 3] with Na[sub 2]Se[sub 5] in 1:2 mole ratio in acetonitrile in the presence of Et[sub 4]NBr afforded (Et[sub 4]N)[sub 3][In[sub 3]Se[sub 3](Se[sub 4])[sub 3]] (VI). Similar reaction of TlCl with Na[sub 2]Se[sub 5] in 1:2 mole ratio in DMF in the presence of Et[sub 4]NBr gave (Et[sub 4]N)[sub 3][Tl[sub 3]Se[sub 3](Se[sub 4])[sub 3]] (VII). 57 refs., 13 figs., 14 tabs.

• OSTI ID: 6265833
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:8; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360602 -- Other Materials-- Structure & Phase Studies
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACETONITRILE
ANIONS
CHALCOGENIDES
CHARGED PARTICLES
CHELATES
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIFFRACTION
HYDROGEN COMPOUNDS
INDIUM COMPOUNDS
INDIUM SELENIDES
IONS
LATTICE PARAMETERS
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
NITRILES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
SCATTERING
SELENIDES
SELENIUM COMPOUNDS
SYNTHESIS
THALLIUM COMPOUNDS
THALLIUM SELENIDES
TRICLINIC LATTICES
WATER
X-RAY DIFFRACTION
YIELDS