Reaction of 1-(dimethylsilyl)-2-silylbenzene with platinum(0) phosphine complex: Isolation and characterization of the Si3-Pt-H complex

Reaction of two equivalents of 1,2-C₆H₄(SiMe₂H)(SiH₃) with Pt(depe)(PEt₃)₂ (depe = Et₂PCH₂CH₂PEt₂) in toluene at room temperature afforded two novel isomeric {1,2-C₆H₄ -(SiMe₂H)(SiH₂)}{1,2-C₆H₄(SiMe₂)(SiH₂)}(H)Pt^IV (depe) complexes 1 and 2 in 5:1 ratio among eight possible isomers. Complex 1 is one of the few examples of tris(silyl)(hydrido)platinum(IV) complexes structurally characterized by single crystal X-ray analysis. The structure of complex 1 was unambiguously determined by multinuclear NMR and single crystal X-ray analysis.     

1,2- and 1,7-Dicarba-closo-dodecarborane(12)platinum(II) complexes formed through metal—carbon σ bonds: cis- and trans-monohydrido derivatives

New neutral platinum(II) monohydridocarborane complexes of general formula cis- and trans-L₂PtH(σ-carb), where L = (C₂H₅)₃P, (C₆H₅)₃P, (C₆H₅)₂(CH₃)P, (C₆H₅)(CH₃)₂P and carb = 2-R-1,2- or 7-R-1,7-B₁₀C₂H₁₀^? (R = H, CH₃, C₆H₅), have been prepared. The configurations of the complexes obtained have been assigned by ¹H NMR spectroscopy. The _cis-monohydridocarborane complexes here reported are the first examples of neutral _cis-monohydrido derivates of platinum(II) containing platinum—carbon σ bonds. ¹H NMR chemical shifts and coupling constants of the prepared complexes are also reported, and used in a tentative evaluation of the _trans-influence of the carbonage ligands.     

Unusual Structure,Fluxionality, and Reaction Mechanism of Carbonyl Hydrosilylation by Silyl Hydride Complex [(ArN)Mo(H)(SiH2Ph)(PMe3)3]

The reactions of bis(borohydride) complexes [(RN?)Mo(BH₄)₂(PMe₃)₂] ( 4 : R=2,6‐Me₂C₆H₃; 5 : R=2,6‐iPr₂C₆H₃) with hydrosilanes afford new silyl hydride derivatives [(RN?)Mo(H)(SiR′₃)(PMe₃)₃] ( 3 : R=Ar, R′₃=H₂Ph; 8 : R=Ar′, R′₃=H₂Ph; 9 : R=Ar, R′₃=(OEt)₃; 10 : R=Ar, R′₃=HMePh). These compounds can also be conveniently prepared by reacting [(RN?)Mo(H)(Cl)(PMe₃)₃] with one equivalent of LiBH₄ in the presence of a silane. Complex 3 undergoes intramolecular and intermolecular phosphine exchange, as well as exchange between the silyl ligand and the free silane. Kinetic and DFT studies show that the intermolecular phosphine exchange occurs through the predissociation of a PMe₃ group, which, surprisingly, is facilitated by the silane. The intramolecular exchange proceeds through a new non‐Bailar‐twist pathway. The silyl/silane exchange proceeds through an unusual Mo^VI intermediate, [(ArN?)Mo(H)₂(SiH₂Ph)₂(PMe₃)₂] ( 19 ). Complex 3 was found to be the catalyst of a variety of hydrosilylation reactions of carbonyl compounds (aldehydes and ketones) and nitriles, as well as of silane alcoholysis. Stoichiometric mechanistic studies of the hydrosilylation of acetone, supported by DFT calculations, suggest the operation of an unexpected mechanism, in that the silyl ligand of compound 3 plays an unusual role as a spectator ligand. The addition of acetone to compound 3 leads to the formation of [trans‐(ArN)Mo(OiPr)(SiH₂Ph)(PMe₃)₂] ( 18 ). This latter species does not undergo the elimination of a Si? O group (which corresponds to the conventional Ojima′s mechanism of hydrosilylation). Rather, complex 18 undergoes unusual reversible β‐CH activation of the isopropoxy ligand. In the hydrosilylation of benzaldehyde, the reaction proceeds through the formation of a new intermediate bis(benzaldehyde) adduct, [(ArN?)Mo(η²‐PhC(O)H)₂(PMe₃)], which reacts further with hydrosilane through a η¹‐silane complex, as studied by DFT calculations.     

Supramolecular architectures in metal(II) (Cd/Zn) halide/nitrate complexes of cytosine/5‐fluorocytosine

Three new metal(II)–cytosine (Cy)/5‐fluorocytosine (5FC) complexes, namely bis(4‐amino‐1,2‐dihydropyrimidin‐2‐one‐κN³)diiodidocadmium(II) or bis(cytosine)diiodidocadmium(II), [CdI₂(C₄H₅N₃O)₂], ( I ), bis(4‐amino‐1,2‐dihydropyrimidin‐2‐one‐κN³)bis(nitrato‐κ²O,O′)cadmium(II) or bis(cytosine)bis(nitrato)cadmium(II), [Cd(NO₃)₂(C₄H₅N₃O)₂], ( II ), and (6‐amino‐5‐fluoro‐1,2‐dihydropyrimidin‐2‐one‐κN³)aquadibromidozinc(II)–6‐amino‐5‐fluoro‐1,2‐dihydropyrimidin‐2‐one (1/1) or (6‐amino‐5‐fluorocytosine)aquadibromidozinc(II)–4‐amino‐5‐fluorocytosine (1/1), [ZnBr₂(C₄H₅FN₃O)(H₂O)]·C₄H₅FN₃O, ( III ), have been synthesized and characterized by single‐crystal X‐ray diffraction. In complex ( I ), the Cd^II ion is coordinated to two iodide ions and the endocyclic N atoms of the two cytosine molecules, leading to a distorted tetrahedral geometry. The structure is isotypic with [CdBr₂(C₄H₅N₃O)₂] [Muthiah et al. (2001). Acta Cryst. E 57 , m558–m560]. In compound ( II ), each of the two cytosine molecules coordinates to the Cd^II ion in a bidentate chelating mode via the endocyclic N atom and the O atom. Each of the two nitrate ions also coordinates in a bidentate chelating mode, forming a bicapped distorted octahedral geometry around cadmium. The typical interligand N—H…O hydrogen bond involving two cytosine molecules is also present. In compound ( III ), one zinc‐coordinated 5FC ligand is cocrystallized with another uncoordinated 5FC molecule. The Zn^II atom coordinates to the N(1) atom (systematic numbering) of 5FC, displacing the proton to the N(3) position. This N(3)—H tautomer of 5FC mimics N(3)‐protonated cytosine in forming a base pair (via three hydrogen bonds) with 5FC in the lattice, generating two fused R₂²(8) motifs. The distorted tetrahedral geometry around zinc is completed by two bromide ions and a water molecule. The coordinated and nonccordinated 5FCs are stacked over one another along the a‐axis direction, forming the rungs of a ladder motif, whereas Zn—Br bonds and N—H…Br hydrogen bonds form the rails of the ladder. The coordinated water molecules bridge the two types of 5FC molecules via O—H…O hydrogen bonds. The cytosine molecules are coordinated directly to the metal ion in each of the complexes and are hydrogen bonded to the bromide, iodide or nitrate ions. In compound ( III ), the uncoordinated 5FC molecule pairs with the coordinated 5FC ligand through three hydrogen bonds. The crystal structures are further stabilized by N—H…O, N—H…N, O—H…O, N—H…I and N—H…Br hydrogen bonds, and stacking interactions.     

Oxo-molybdenum(IV) and tungsten(IV) complexes with phosphine and isocyanide ligands

The complexes [MOCl₂(dmpe)(PMe₃)] and [MOCl₂(dmpe)₂]Cl (M = Mo, W; dmpe = Me₂PCH₂CH₂PMe₂) have been prepared by reaction of the oxo compounds [MOCl₂(PMe₃)₃] with equivalent amounts of the dmpe ligand under appropriate conditions. The dark blue tungsten species [WOCl₂(dmpe)(PMe₃)] forms only slowly but reacts readily with more dmpe to afford [WOCl(dmpe)₂]Cl. This prevents isolation of the former in a pure form. The related isocyanide derivatives [MOCl₂(CNR)(PMe₃)₂], (M = Mo; R = CMe₃ and C₆H₁₁; M = W, R = CMe₃) have been obtained similarly by reaction of the [MOCl₂(PMe₃)₃] complexes with the stoichiometric amount of the isocyanide ligand, but attempts to prepare the carbonyl analogues, [MOCl₂(CO)(PMe₃)₂], have proved unsuccessful. The new compounds have been characterized by analytical and spectroscopic methods (IR, ¹H, ¹³C and ¹³P NMR spectroscopy).     

Hydrogen‐bonded chains in three cis‐dichloridoplatinum(II) complexes bearing piperidine and amine ligands

The crystal structures of cis‐dichlorido(ethylamine‐κN)(piperidine‐κN)platinum(II), [PtCl₂(C₂H₇N)(C₅H₁₁N)], (I), cis‐dichlorido(3‐methoxyaniline‐κN)(piperidine‐κN)platinum(II), [PtCl₂(C₅H₁₁N)(C₇H₉NO)], (II), and cis‐dichlorido(piperidine‐κN)(quinoline‐κN)platinum(II), [PtCl₂(C₅H₁₁N)(C₉H₇N)], (III), have been determined at 100 K in order to verify the influence of the nonpiperidine ligand on the geometry and crystal packing. The crystal packing is characterized by N—H...Cl hydrogen bonding, resulting in the formation of chains of molecules connected in a head‐to‐tail fashion. Hydrogen‐bonding interactions play a major role in the packing of (I), where the chains further aggregate into planes, but less so in the case of (II) and (III), where π–π stacking interactions are of greater importance.     

μ‐1,2‐Bis(4‐pyridyl)ethene‐κ2N:N′‐bis(tetraaqua­{4‐[2‐(4‐pyridinio)­ethenyl]pyridine‐κN}cobalt(II)) hexaaqua­cobalt(II) tetrakis(sulfate) octahydrate

The title compound, [Co₂(C₁₂H₁₁N₂)₂(C₁₂H₁₀N₂)(H₂O)₈][Co(H₂O)₆](SO₄)₄·8H₂O, consists of bis(4‐pyridyl)ethenedicobalt(II) cations, hexaaqua­cobalt cations, sulfate anions and water solvent molecules that are linked by hydrogen bonds into a network structure. In the hexaaquacobalt cation, the six water molecules are coordinated in an octahedral geometry to the Co atom, which lies on an inversion centre. The other cation is a 1,2‐bis(4‐pyridyl)ethene‐bridged centrosymmetric dimer, consisting of protonated 1,2‐bis(4‐pyridyl)­ethene cations, a bridging 1,2‐bis(4‐pyridyl)ethene ligand and tetraaqua­cobalt cations. Each Co atom is six‐coordinated by four water molecules and two N atoms from a protonated 1,2‐bis(4‐pyridyl)ethene cation and the bridging 1,2‐bis(4‐pyridyl)­ethene ligand, and the geometry around each Co atom is octahedral.     

Crystal structure and DFT calculations of Cp2NbH(SiIMe2)(SiFMe2): an asymmetric bis(silyl) niobocene hydride complex

An asymmetric bis(silyl) niobocene hydride complex, namely, bis(η⁵-cyclopentadienyl)(fluorodimethylsilyl)hydrido(iododimethylsilyl)niobium, [Nb(C₅H₅)₂(C₂H₆FSi)(C₂H₆ISi)H] or Cp₂NbH(SiIMe₂)(SiFMe₂), has been studied to determine the effect of the silyl ligand on the position of the hydride attached to the Nb atom. It has been shown that when a Group 17 atom is substituted onto one of the silyl ligands, there is a greater interaction between the hydride and this ligand, as demonstrated by a shorter Si…H distance. In the present work, we have investigated the effect when the silyl ligands are substituted by different Group 17 atoms. We present here the structure and DFT calculations of Cp₂NbH(SiIMe₂)(SiFMe₂), showing that the position of the hydride is located between the two silyl ligands. The results from our investigation show that the hydride is closer to the silyl ligand that is substituted by fluorine.     

(η3‐Allyl‐2κ3C)(chloro‐1κCl)(μ‐N,N′‐diethyldithioxamidato‐1:2κ4S,S′:N,N′)[diphenyl(2‐pyridyl)phosphine‐1κP]palladium(II)platinum(II) chloroform solvate

The title compound, [PdPtCl(C₃H₅)(C₆H₁₀N₂S₂)(C₁₇H₁₄NP)]·CHCl₃, was obtained by deprotonation of the initial platinum(II) complex of the di­thio­xamide and subsequent reaction with [Pd(η³‐C₃H₅)(μ‐Cl)]₂. Both metal atoms exhibit a square‐planar coordination geometry, with the two planes forming a dihedral angle of 21.7 (2)°. The di­thio­xamide bis‐chelating bridge is flat.     

Synthesis and Analysis of the Structure,Diffusion and Cytotoxicity of Heterocyclic Platinum(IV) Complexes

We have developed six dihydroxidoplatinum(IV) compounds with cytotoxic potential. Each derived from active platinum(II) species, these complexes consist of a heterocyclic ligand (H_L) and ancillary ligand (A_L) in the form [Pt(H_L)(A_L)(OH)₂]²⁺, where H_L is a methyl‐functionalised variant of 1,10‐phenanthroline and A_L is the S,S or R,R isomer of 1,2‐diaminocyclohexane. NMR characterisation and X‐ray diffraction studies clearly confirmed the coordination geometry of the octahedral platinum(IV) complexes. The self‐stacking of these complexes was determined using pulsed gradient stimulated echo nuclear magnetic resonance. The self‐association behaviour of square planar platinum(II) complexes is largely dependent on concentration, whereas platinum(IV) complexes do not aggregate under the same conditions, possibly due to the presence of axial ligands. The cytotoxicity of the most active complex, exhibited in several cell lines, has been retained in the platinum(IV) form.     

A ferrocenyl‐substituted pseudo­titanocene complex

The title compound, (η⁵‐cyclo­penta­dienyl)[(1,2,3,4,5‐η)‐4‐ferro­cenyl‐1,2,5,6‐tetrakis­(tri­methyl­silyl)­cyclo­hexa‐2,4‐dien‐1‐yl]­titanium(II), [TiFe(C₅H₅)₂(C₂₃H₄₂Si₄)] or [Ti{η⁵‐C₆H₂{Fe­(η⁵‐C₅H₄)(η⁵‐C₅H₅)}{Si(CH₃)₃}₄}(η⁵‐C₅H₅)], possesses two directly linked metallocene units that subtend an angle of 52.9 (1)° (defined by the least‐squares planes of the directly connected π‐ligands) associated with the steric requirements of the bulky tri­methyl­silyl substituents. The cyclo­hexa­dienyl ligand adopts an envelope conformation; the perpendicular distance of its η⁵‐plane to the Ti atom is 1.512 (1) Å.     

Cationic,neutral and anionic metal(II) complexes derived from 4‐oxo‐4H‐pyran‐2,6‐dicarboxylic acid (chelidonic acid)

The structures of five metal complexes containing the 4‐oxo‐4H‐pyran‐2,6‐dicarboxylate dianion illustrate the remarkable coordinating versatility of this ligand and the great structural diversity of its complexes. In tetraaquaberyllium 4‐oxo‐4H‐pyran‐2,6‐dicarboxylate, [Be(H₂O)₄](C₇H₂O₆), (I), the ions are linked by eight independent O—H...O hydrogen bonds to form a three‐dimensional hydrogen‐bonded framework structure. Each of the ions in hydrazinium(2+) diaqua(4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)calcate, (N₂H₆)[Ca(C₇H₂O₆)₂(H₂O)₂], (II), lies on a twofold rotation axis in the space group P2/c; the anions form hydrogen‐bonded sheets which are linked into a three‐dimensional framework by the cations. In bis(μ‐4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)bis[tetraaquamanganese(II)] tetrahydrate, [Mn₂(C₇H₂O₆)₂(H₂O)₈]·4H₂O, (III), the metal ions and the organic ligands form a cyclic centrosymmetric Mn₂(C₇H₂O₆)₂ unit, and these units are linked into a complex three‐dimensional framework structure containing 12 independent O—H...O hydrogen bonds. There are two independent Cu^II ions in tetraaqua(4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)copper(II), [Cu(C₇H₂O₆)(H₂O)₄], (IV), and both lie on centres of inversion in the space group P; the metal ions and the organic ligands form a one‐dimensional coordination polymer, and the polymer chains are linked into a three‐dimensional framework containing eight independent O—H...O hydrogen bonds. Diaqua(4‐oxo‐4H‐pyran‐2,6‐dicarboxylato)cadmium monohydrate, [Cd(C₇H₂O₆)(H₂O)₂]·H₂O, (V), forms a three‐dimensional coordination polymer in which the organic ligand is coordinated to four different Cd sites, and this polymer is interwoven with a complex three‐dimensional framework built from O—H...O hydrogen bonds.     

(n‐Butyl­di­phenyl­phosphine)­di­chloro(η6‐p‐cymeme)­ruthenium(II)

The title ruthenium complex, [RuCl₂(C₁₀H₁₄)(C₁₆H₁₉P)], contains a monodentate (C₄H₉)PPh₂ ligand coordinated by the P atom. Coordination about the metal centre is completed by a η⁶‐p‐cymene ligand and two Cl atoms.     

Platinum complexes of oxopurines: cis‐bis(theophyllinato‐N7)bis(triphenylphosphine)platinum(II) and cis‐chloro(theobrominato‐N1)bis(triphenylphosphine)platinum(II) ethanol hemisolvate

The syntheses and structures of two mixed‐ligand complexes of platinum(II) with deprotonated oxopurine bases and tri­phenyl­phosphine are reported, namely the theophyllinate complex cis‐bis(1,2,3,6‐tetra­hydro‐1,3‐di­methyl­purine‐2,6‐dionato‐κN⁷)­bis(tri­phenyl­phosphine‐κP)­platinum(II), [Pt(C₇H₇N₄O₂)₂(C₁₈H₁₅P)₂], (I), and the theobrominate complex cis‐chloro(1,2,3,6‐tetrahydro‐3,7‐dimethylpurine‐2,6‐dionato‐κN¹)­bis(tri­phenyl­phosphine‐κP)­platinum(II) ethanol hemisolvate, [PtCl(C₇H₇N₄O₂)(C₁₈H₁₅P)₂]·0.5C₂H₅OH, (II). In (I), the coordination geometry of Pt is square planar, formed by the two coordinating N atoms of the theophyl­linate anions in a cis arrangement and two P atoms from the tri­phenyl­phosphine groups. In (II), there are two crystallographically independent mol­ecules. They both exhibit a square‐planar coordination geometry around Pt involving one Cl atom, the coordinating N atom of the theobrominate anion and two P atoms from the tri­phenyl­phosphine groups. The two tri­phenyl­phosphine groups are arranged in a cis configuration in both structures. The heterocyclic rings are rotated with respect to the coordination plane of the metal by 82.99 (8) and 88.09 (8)° in complex (I), and by 85.91 (16) and 88.14 (18)° in complex (II). Both structures are stabilized by intramolecular stacking interactions involving the purine rings and the phenyl rings of adjacent tri­phenyl­phosphine moieties.     

Insight into the structures of [M(C5H4I)(CO)3] and [M2(C12H8)(CO)6] (M = Mn and Re) containing strong I...O and π(CO)–π(CO) interactions

The compounds tricarbonyl(η⁵‐1‐iodocyclopentadienyl)manganese(I), [Mn(C₅H₄I)(CO)₃], (I), and tricarbonyl(η⁵‐1‐iodocyclopentadienyl)rhenium(I), [Re(C₅H₄I)(CO)₃], (III), are isostructural and isomorphous. The compounds [μ‐1,2(η⁵)‐acetylenedicyclopentadienyl]bis[tricarbonylmanganese(I)] or bis(cymantrenyl)acetylene, [Mn₂(C₁₂H₈)(CO)₆], (II), and [μ‐1,2(η⁵)‐acetylenedicyclopentadienyl]bis[tricarbonylrhenium(I)], [Re₂(C₁₂H₈)(CO)₆], (IV), are isostructural and isomorphous, and their molecules display inversion symmetry about the mid‐point of the ligand C[triple‐bond]C bond, with the (CO)₃M(C₅H₄) (M = Mn and Re) moieties adopting a transoid conformation. The molecules in all four compounds form zigzag chains due to the formation of strong attractive I...O [in (I) and (III)] or π(CO)–π(CO) [in (I) and (IV)] interactions along the crystallographic b axis. The zigzag chains are bound to each other by weak intermolecular C—H...O hydrogen bonds for (I) and (III), while for (II) and (IV) the chains are bound to each other by a combination of weak C—H...O hydrogen bonds and π(Csp²)–π(Csp²) stacking interactions between pairs of molecules. The π(CO)–π(CO) contacts in (II) and (IV) between carbonyl groups of neighboring molecules, forming pairwise interactions in a sheared antiparallel dimer motif, are encountered in only 35% of all carbonyl interactions for transition metal–carbonyl compounds.     

Activation of 1, 2‐Dihydrodisilanes at Platinum(0) Phosphine Complexes: Syntheses and Structures of Bissilyl Platinum(II) Complexes

The bissilyl complexes 3 – 6 were synthesized by reactions of the platinum(0) complexes [Pt(η²‐C₂H₄)(diphos)] ( 1 : diphos = dppe; 2 : diphos = dcpe) with the disilanes 1, 1,2, 2‐tetramethyldisilane and 1, 1,2, 2‐tetraphenyldisilane via Si–Si bond activation. The molecular structures of 4 and 5 in the solid state are reported. The reaction of 2 with HPh₂SiSiPh₂H led to the immediate formation of the hydrido disilanyl complex [Pt(H)(SiPh₂SiPh₂H)(dcpe)] ( 7 ), which converts slowly into the bissilyl complex [Pt(SiHPh₂)₂(dcpe)] ( 6 ). The latter was reported before to be a η²‐disilene complex.     

An indium(III)–water chain based on an unusual acyclic water pentamer

An in situ reaction under hydro­thermal conditions leads to the formation of the title compound, diaqua­(pyridine‐2‐carboxyl­ato)­(pyridine‐2,6‐dicarboxyl­ato)indium(II) trihydrate, [In(C₆H₄NO₂)(C₇H₃NO₄)(H₂O)₂]·3H₂O, in which the central In^III atom is seven‐coordinated by one pyridine‐2,6‐di­carboxyl­ate ligand, one pyridine‐2‐carboxyl­ate ligand and two water mol­ecules in a penta­gonal–bipyramidal coordination environment. An indium(III)–water chain based on an unusual water pentamer is observed.     

Aqua­bis(3‐meth­oxy‐2‐pyridonato)­(2,2′:6′,2′′‐terpyridine)ruthenium(II)–acetonitrile–water (1/1/1)

The title compound, [Ru(C₆H₆NO₂)₂(C₁₅H₁₁N₃)(H₂O)]·CH₃CN·H₂O, is a transfer hydrogenation catalyst supported by nitro­gen‐donor ligands. This octa­hedral Ru^II complex features rare monodentate coordination of 3‐meth­oxy‐2‐pyridonate ligands and inter­ligand S(6)S(6) hydrogen bonding. Comparison of the title complex with a structural analog with unsubstituted 2‐pyridonate ligands reveals subtle differences in the orientation of the ligand planes.     

Ta(CNDipp)6: An Isocyanide Analogue of Hexacarbonyltantalum(0)

Hexakis(2,6‐diisopropylphenylisocyanide)tantalum is the first isocyanide analogue of the highly unstable Ta(CO)₆ and represents the only well‐defined zerovalent tantalum complex to be prepared by conventional laboratory methods. Two prior examples of homoleptic Ta⁰ complexes are known, Ta(benzene)₂ and Ta(dmpe)₃, dmpe=1,2‐bis(dimethylphosphano)ethane, but these have only been accessed via ligand co‐condensation with tantalum vapor in a sophisticated metal‐atom reactor. Consistent with its 17‐electron nature, Ta(CNDipp)₆ undergoes facile one‐electron oxidation, reduction, or disproportionation reactions. In this sense, it qualitatively resembles V(CO)₆, the only paramagnetic homoleptic metal carbonyl isolable under ambient conditions.     

Zinc(II) and Nickel(II) Complexes Based on Schiff Base Ligands: Synthesis,Crystal Structure,Luminescent and Magnetic Properties

Three new phenolate oxygen bridged transition metal complexes [Zn₃(HL¹)₃(μ₃‐CH₃O)]·(ClO₄)₂(H₂O)₃ ( 1 ), [Ni₂(HL¹)₂(μ_1,1‐N₃)(o‐vanillin)]·H₂O ( 2 ), [Ni₃(HL²)₂(PhCOO)₂(PhCOOH)₂(EtOH)₂] ( 3 ) have been synthesized by metal ions and potentially multidentate Schiff base ligands (H₂L¹ = 2‐((1‐hydroxy‐2‐methylpropan‐2‐ylimino) methyl)‐6‐methoxyphenol; H₃L² = (E)‐1‐((2‐hydroxy‐3‐methoxy‐benzylidene)amino)ethane‐1,2‐diol). All the three complexes 1 , 2 , and 3 have been characterized by elemental analysis, FT‐IR spectroscopy, and single‐crystal X‐ray diffraction studies. Crystal structures reveal that complex 1 is a trinuclear incomplete cubane‐like zinc cluster whereas complex 2 is a dinuclear nickel complex bridged by azide, and compound 3 is a trinuclear nickel complex. The luminescent property for complex 1 and magnetic behaviors for complexes 2 and 3 have been investigated.