Polynuclear manganese complexes with the dicarboxylate ligand m-phenylenedipropionate: a hexanuclear mixed-valence (3Mn(III), 3Mn(IV)) complex.

The dicarboxylate group m-phenylenedipropionate (mpdp(2)(-)) has been used for the synthesis of four new Mn compounds of different nuclearities and oxidation states: [Mn(2)O(mpdp)(bpy)(2)(H(2)O)(MeCN)](ClO(4))(2) (3), [Mn(3)O(mpdp)(3)(py)(3)](ClO(4)) (4), [Mn(3)O(mpdp)(3)(py)(3)] (5), and [Mn(6)O(7)(mpdp)(3)(bpy)(3)](ClO(4)) (6). Compound 3 (2Mn(III)) contains a [Mn(2)(micro-O)](4+) core, whereas 5 (Mn(II), 2Mn(III)) and 4 (3Mn(III)) contain the [Mn(3)(micro(3)-O)](6+,7+) core, respectively. In all three compounds, the mpdp(2)(-) ligand is flexible enough to adopt the sites occupied by two monocarboxylates in structurally related compounds, without noticeable distortion of the cores.

Heptanuclear and decanuclear manganese complexes with the anion of 2-hydroxymethylpyridine.

The synthesis and magnetic properties are reported of two new clusters [Mn(10)O(4)(OH)(2)(O(2)CMe)(8)(hmp)(8)](ClO(4))(4) (1) and [Mn(7)(OH)(3)(hmp)(9)Cl(3)](Cl)(ClO(4)) (2). Complex 1 was prepared by treatment of [Mn(3)O(O(2)CMe)(6)(py)(3)](ClO(4)) with 2-(hydroxymethyl)pyridine (hmpH) in CH(2)Cl(2), whereas 2 was obtained from the reaction of MnCl(2).4H(2)O, hmpH, and NBu(n)(4)MnO(4) in MeCN followed by recrystallization in the presence of NBu(n)(4)ClO(4).

Symmetric and asymmetric dinuclear manganese(IV) complexes possessing a [MnIV2(mu-O)2(muO2CMe)]3+ core and terminal Cl- ligands.

The synthesis of new dinuclear manganese(IV) complexes possessing the [Mn(IV)(2)(mu-O)(2)(mu-O(2)CMe)](3+) core and containing halide ions as terminal ligands is reported. [Mn(2)O(2)(O(2)CMe)Cl(2)(bpy)(2)](2)[MnCl(4)] (1; bpy = 2,2'-bipyridine) was prepared by sequential addition of [MnCl(3)(bpy)(H(2)O)] and (NBzEt(3))(2)[MnCl(4)] to a CH(2)Cl(2) solution of [Mn(3)O(4)(O(2)CMe)(4)(bpy)(2)]. The complex [Mn(IV)(2)O(2)(O(2)CMe)Cl(bpy)(2)(H(2)O)](NO(3))(2) (2) was obtained from a water/acetic acid solution of MnCl(2).

Single-molecule magnets: a new family of Mn(12) clusters of formula [Mn(12)O(8)X(4)(O(2)CPh)(8)L(6)].

The reaction of (NBu(n)(4))[Mn(8)O(6)Cl(6)(O(2)CPh)(7)(H(2)O)(2)] (1) with 2-(hydroxymethyl)pyridine (hmpH) or 2-(hydroxyethyl)pyridine (hepH) gives the Mn(II)(2)Mn(III)(10) title compounds [Mn(12)O(8)Cl(4)(O(2)CPh)(8)(hmp)(6)] (2) and [Mn(12)O(8)Cl(4)(O(2)CPh)(8)(hep)(6)] (3), respectively, with X = Cl. Subsequent reaction of 3 with HBr affords the Br(-) analogue [Mn(12)O(8)Br(4)(O(2)CPh)(8)(hep)(6)] (4). Complexes 2.

Dinuclear and Hexanuclear Iron(III) Oxide Complexes with a Bis(bipyridine) Ligand: A New [Fe(6)(&mgr;(3)-O)(4)](10+) Core.

The use of the bis(bipyridine) ligand L (1,2-bis(2,2'-bipyridyl-6-yl)ethane) has yielded new dinuclear and hexanuclear complexes. The FeCl(3)/NaO(2)CPh/L (4:4:1) reaction system in MeCN gives red-brown [Fe(6)O(4)Cl(4)(O(2)CPh)(4)L(2)][FeCl(4)](2) (1). The same reaction system in a 3:3:1 ratio in MeOH gives orange [Fe(2)(OMe)(2)Cl(2)(O(2)CPh)L][FeCl(4)] (2).

Dinuclear (d(3)-d(3)) Diolate Complexes of Molybdenum and Tungsten. 3.(1) Bridging and Chelating Isomers of M(2)(NMe(2))(2)(O approximately approximately CHMe approximately approximately O)(2), Where O approximately approximately CHMe approximately approximately O Is the Dianion of 2,2'-Ethylidenebis(4,6-di-tert-butylphenol). Kinetic versus Thermodynamic Considerations.

Hydrocarbon solutions of Mo(2)(NMe(2))(6) and 2,2'-ethylidenebis(4,6-di-tert-butylphenol), HO approximately approximately CHMe approximately approximately OH (2 equiv), react to give a mixture of two isomers, A and B, of formula Mo(2)(NMe(2))(2)(O approximately approximately CHMe approximately approximately O)(2). Both A and B are shown to contain the bridging &mgr;-O approximately approximately CHMe approximately approximately O ligands. They are diastereomers differing with respect to the positioning of the CHMe moiety as a result of ring closure with elimination of HNMe(2).

Syntheses, Structures, and Thermal Behavior of Cu(hfacac) Complexes Derived from Ethanolamines.

A series of novel precursors for MOCVD of metallic copper have been synthesized and structurally characterized. These precursors are composed of Cu(hfacac)(2), which serves as a volatile source of Cu, and amino alcohols, which act as reductants and anchor firmly to the copper center through the amine unit. In some cases, a proton transfer from the coordinated alcohol to the hfacac ligand results in the formation of an alkoxide unit and the release of the free Hhfacac.

Tetranuclear and Pentanuclear Vanadium(IV/V) Carboxylate Complexes: [V(4)O(8)(NO(3))(O(2)CR)(4)](2-) and [V(5)O(9)X(O(2)CR)(4)](2-) (X = Cl(-), Br(-)) Salts.

The syntheses and properties of tetra- and pentanuclear vanadium(IV,V) carboxylate complexes are reported. Reaction of (NBzEt(3))(2)[VOCl(4)] (1a) with NaO(2)CPh and atmospheric H(2)O/O(2) in MeCN leads to formation of (NBzEt(3))(2)[V(5)O(9)Cl(O(2)CPh)(4)] 4a; a similar reaction employing (NEt(4))(2)[VOCl(4)] (1b) gives (NEt(4))(2)[V(5)O(9)Cl(O(2)CPh)(4)] (4b). Complex 4a.

Tetranuclear and Octanuclear Manganese Carboxylate Clusters: Preparation and Reactivity of (NBu(n)(4))[Mn(4)O(2)(O(2)CPh)(9)(H(2)O)] and Synthesis of (NBu(n)(4))(2)[Mn(8)O(4)(O(2)CPh)(12)(Et(2)mal)(2)(H(2)O)(2)] with a "Linked-Butterfly" Structure.

The reaction of Mn(O(2)CPh)(2).2H(2)O and PhCO(2)H in EtOH/MeCN with NBu(n)(4)MnO(4) gives (NBu(n)(4))[Mn(4)O(2)(O(2)CPh)(9)(H(2)O)] (4) in high yield (85-95%). Complex 4 crystallizes in monoclinic space group P2(1)/c with the following unit cell parameters at -129 degrees C: a = 17.

Structural, Spectroscopic, and Magnetochemical Characterization of the Trinuclear Vanadium(III) Carboxylates [V(3)O(O(2)CR)(6)L(3)](ClO(4)) (R = Various Groups; L = Pyridine, 4-Picoline, 3,5-Lutidine).

Synthetic procedures are described that allow access to the [V(3)O(O(2)CR)(6)L(3)](ClO(4)) (R = various groups; L = pyridine (py), 4-picoline (pic) or 3,5-lutidine (lut)) family of complexes. Treatment of VCl(3)(THF)(3) with NaO(2)CR (R = Me, Et) in RCO(2)H/py, pic/MeCN, or CH(2)Cl(2) solution followed by addition of NBu(n)(4)ClO(4) leads to isolation of [V(3)O(O(2)CR)(6)L(3)](ClO(4)) salts in 47-95% yields. A similar procedure for R = C(6)H(5), C(6)H(4)-p-OMe, C(6)H(3)-m-Me(2), and C(6)H(4)-p-Cl but omitting addition of NaO(2)CR provides the corresponding benzoate or substituted-benzoate derivatives in 24-56% yields.