Self-assembly of a Pd-II neutral molecular rectangle via a new organometallic Pd-2(II) molecular clip and oxygen donor linker

Two components self-assembly of a Pd-4 neutral molecular rectangle driven by Pd-O bond coordination has been achieved and this pi-electron rich rectangle shows fluorescence quenching in presence of nitroaromatics, which are the chemical signatures of many explosives.

CO adsorption on ionic Pt, Pd and Cu sites in Ce(1-x)M(x)O(2-delta) (M = Pt(2+), Pd(2+), Cu(2+))

Noble metal ion substituted CeO(2) in the form of Ce(0.98)M(0.02)O(2-delta) solid solution (where M = Pt, Pd, Cu) are the new generation catalysts with applications in three-way exhaust catalysis. While adsorption of CO on noble metals ions is well-known, adsorption of CO on noble metal ions has not been studied because creating exclusive ionic sites has been difficult. Using first-principles density functional theory (DFT) we have shown that CO gets adsorbed on the noble metal Pt(2+), Pd(2+), Cu(2+) ionic sites in the respective compounds, and the net energy of the overall system decreases. Adsorption of CO on metal ions is also confirmed by Fourier transform infrared spectroscopy (FTIR).

Direct evidence of redox interaction between metal ion and support oxide in Ce(0.98)Pd(0.02)O(2-delta) by a combined electrochemical and XPS study

A combined electrochemical method and X-ray photo electron spectroscopy (XPS) has been utilized to understand the Pd(2+)/CeO(2) interaction in Ce(1-x)Pd(x)O(2-delta) (x = 0.02). A constant positive potential (chronoamperometry) is applied to Ce(0.98)Pd(0.02)O(2-delta) working electrode which causes Ce(4+) to reduce to Ce(3+) to the extent of similar to 35%, while Pd remains in the +2 oxidation state. Electrochemically cycling this electrode between 0.0-1.2 V reverts back to the original state of the catalyst. This reversibility is attributed to the reversible reduction of Ce(4+) to Ce(3+) state. CeO(2) electrode with no metal component reduces to CeO(2-y) (y similar to 0.4) after applying 1.2 V which is not reversible and the original composition of CeO(2) cannot be brought back in any electrochemical condition. During the electro-catalytic oxygen evolution reaction at a constant 1.2 V for 1000 s, Ce(0.98)Pd(0.02)O(2-delta) reaches a steady state composition with Pd in the +2 states and Ce(4+) : Ce(3+) in the ratio of 0.65 : 0.35. This composition can be denoted as Ce(0.63)(4+)Ce(0.35)(4+)Pd(0.02)O(2-delta-y) (y similar to 0.17). When pure CeO(2) is put under similar electrochemical condition, it never reaches the steady state composition and reduces almost to 85%. Thus, Ce(0.98)Pd(0.02)O(2-delta) forms a stable electrode for the electro-oxidation of H(2)O to O(2) unlike CeO(2) due to the metal support interaction.

Mono- and Dialkyne Insertion Reactions of Cyclopalladated N,N `,N `'-Triarylguanidines kappa(2)(C,N)Pd(mu-Br)](2) and cis-/trans-kappa(2)(C,N)Pd(Lewis Base)Br]. Scaffolds for Enlarged, Rearranged, and Zwitterionic Palladacycles through Ring Contraction cum Amine-Imine Tautomerization

Insertion reactions of six-membered cyclopalladated N,N',N''-triarylguanidines, kappa(2)(C,N)Pd(mu-Br)](2) with various alkynes in CH2Cl2 under ambient conditions afforded diinserted eight-membered palladacycles, (kappa(2)(C,N):eta(2)(C=C)-PdBr] (1-11), in high yield (76-96%), while insertion reactions of six-membered cyclopalladated N,N',N''-triarylguanidines, kappa(2)(C,N)Pd(Lewis base)Br] (VI-XI), with various alkynes under the aforementioned conditions afforded monoinserted six-membered palladacycles, kappa(2)(C,N)-Pd(Lewis base)Br] (12-21), in high yield (81-91%) except for 14 (23%). The insertion reaction of VI with 2 equiv of dimethyl acetylenedicarboxylate (DMAD) and the insertion reaction of 12 with 1 equiv of DMAD in CH2Cl2 under ambient conditions resulted in the formation of a diinserted zwitterionic five-membered palladacycle, kappa(2)(C,C)Pd(2,6-lutidine)Br] (22), in 76% and 70% yields, respectively. Palladacycle 22 upon reaction with AgOTf in wet MeCN afforded the ionic palladacycle kappa(2)(C,C)Pd(2,6-lutidine)(H2O)]OTf] (23) in 78% yield. The ring size of the ``kappa(2)(C,N)Pd]'' unit in the structurally characterized diinserted palladacycles (1 center dot 2CH(2)Cl(2)center dot H2O, 2, 5, and 7), and monoinserted palladacycles (17, 18, and 20 center dot C7H8 H2O) is smaller than that anticipated for mono- and diinserted palladacycles, and this feature is mainly ascribed to the proclivity of III-XI to undergo ring contraction cum amine-imine tautomerization upon alkyne insertion. Palladacycle 22 represents the first diinserted product obtained in alkyne insertion reactions of kappa(2)(C,N)Pd(Lewis base)X] type palladarycles. The molecular structure of 22 center dot H2O determined by X-ray diffraction indicates that the positive charge on the guanidinium moiety is balanced by the negative charge on the palladium atom and thus represents the first structurally characterized zwitterionic palladacycle to be reported in alkyne insertion chemistry. Plausible mechanisms of formation of 12-21 and 22 have been outlined. The presence of more than one species in solution for some of the palladacycles in the series 1-7 and 12-21 was explained by invoking the C-N single-bond rotation of the CN3 unit of the guanidine moiety, while this process in conjunction with Pd-N(lutidine) bond rotation was invoked to explain the presence of four isomers of 15, as studied with the aid of variable-concentration H-1 NMR experiments carried out for 14 and 15.

Molecular complexes of metallo tetraphenyl porphyrins with 2,4,5,7-tetranitro fluorenone

The interactions of mesotetraphenyl porphyrin and its metallo derivatives with 2,4,5,7-tetra nitrofluorenone have been studied using spectroscopic methods. The association constants (K) for 1:1 complexes in Ch2Cl2Cl2 follow the order Pd+2>Co+2> Cu+2>VO+2>Ni+2>Zn+2. The values of K are accounted in terms of stereochemistry of MTPPs and the electronic configuration of the metal ions. The magnitude and direction of the proton NMR shifts of the acceptor and donor in the complexes and their ESR parameter furnish information as to the possible structures of these complexes in solution.

Molecular-complexes of metallo tetraphenyl porphyrins with 2,4,5,7-tetranitro fluorenone

The interactions of mesotetraphenyl porphyrin and its metallo derivatives with 2,4,5,7-tetra nitrofluorenone have been studied using spectroscopic methods. The association constants (K) for 1:1 complexes in Ch2Cl2Cl2 follow the order Pd+2>Co+2> Cu+2>VO+2>Ni+2>Zn+2. The values of K are accounted in terms of stereochemistry of MTPPs and the electronic configuration of the metal ions. The magnitude and direction of the proton NMR shifts of the acceptor and donor in the complexes and their ESR parameter furnish information as to the possible structures of these complexes in solution.

Self-assembly of neutral and cationic Pd-II organometallic molecular rectangles: synthesis, characterization and nitroaromatic sensing

Design and synthesis of three novel 2 + 2] self-assembled molecular rectangles 1-3 via coordination driven self-assembly of predesigned Pd(II) ligands is reported. 1,8-Diethynylanthracene was assembled with trans-Pd(PEt3)(2)Cl-2 in the presence of CuCl catalyst to yield a neutral rectangle 1 via Pd-C bond formation. Complex 1 represents the first example of a neutral molecular rectangle obtained via C-Pd coordination driven self-assembly. A new Pd-2(II) organometallic building block with 180 degrees bite-angle 1,4-bistrans-(ethynyl)Pd(PEt3)(2)(NO3)] benzene (M-2) containing ethynyl functionality was synthesized in reasonable yield by employing Sonagashira coupling reaction. Self-assembly of M-2 with two organic clip-type donors (L-2-L-3) afforded 2 + 2] self-assembled molecular rectangles 2 and 3, respectively L-2 = 1,8-bis(4-pyridylethynyl) anthracene; L-3 = 1,3-bis(3-pyridyl) isophthalamide]. The macrocycles 1-3 were fully characterized by multinuclear NMR and ESI-MS spectroscopic techniques, and in case of 1 the structure was unambiguously determined by single crystal X-ray diffraction analysis. Incorporation of Pd-ethynyl bonds helped to make the assemblies p-electron rich and fluorescent in nature. Complexes 1-2 showed quenching of fluorescence intensity in solution in presence of nitroaromatics, which are the chemical signatures of many commercially available explosives.

Organometallic chemistry of diphosphazanes .13. Palladium complexes of unsymmetrical diphosphazanes Ph(2)PN(Pr-i)PYY'

Unsymmetrical diphosphazanes Ph(2)PN(Pr-i)PYY' [YY' = O2C12H8 (L(1)), O2C20H12 (L(2)); Y = Ph and Y' = OC6H4Br-4 (L(3)), OC(6)H(4)Me-4 (L(4)), OC(6)H(3)Me(2)-3,5 (L(5)), N(2)C(3)HMe(2)-3,5 (L(6))] react with cis-[PdCl2(COD)] (COD = cycloocta-1,5-diene) giving the chelate complexes of the type cis-[PdCl2{eta(2)-Ph(2)PN(Pr-i)PYY'}] [YY' = O2C12H8 (1), O2C20H12 (2), Y = Ph and Y' = OC6H4Br-4 (3), OC(6)H(4)Me-4 (4), OC(6)H(3)Me(2)-3,5 (5), N(2)C(3)HMe(2)-3,5 (6)]. The P-N bond in 3 and 5 undergoes a facile cleavage in methanol solution to give cis-[PdCl2{eta(1)Ph(2)P(OMe)}{eta(1)-PhP(NHPri)(Y')}] [Y' = OC6H4Br-4 (7), OC(6)H(3)Me(2)-3,5 (8)]. Reactions of Pd-2(dba)(3) . CHCl3 (dba = dibenzylideneacetone) with the diphosphazanes Ph(2)PN(Pr-i)PPhY' [Y' = OC(6)H(4)Me-4 (L(4)), N(2)C(3)HMe(2)-3,5 (L(6)), N2C3H3 (L(7))] in the presence of MeI yields cis-[PdI2{eta(2)-Ph(2)PN(Pr-i)PPhMe}] (9); the P-O or P-N(pyrazolyl) bond of the starting ligands is cleaved and a p-C(Me) bond is formed. An analogous oxidative addition reaction in the presence of Ph(2)PN(Pr-i)PPh(2) (L(8)) yields cis-[PdI(Me)(eta(2)-L(8))] (10) and cis-[PdI2(eta 2-L(8))] (11). The structures of 8 and 9 have been determined by X-ray diffraction. Copyright (C) 1996 Elsevier Science Ltd

A DMFC with Methanol-Tolerant-Carbon-Supported-Pt-Pd-Alloy Cathode

Methanol-tolerant Pt-Pd alloy catalysts supported on to carbon with varying Pt:Pd atomic ratios of 1:1, 2:1 and 3:1 are prepared by a novel wet-chemical method and characterized using powder XRD, XPS, FESEM, EDAX and TEM techniques. The optimum atomic weight ratio for Pt to Pd in the carbon-supported alloy catalyst as established by linear-sweep voltammetry (LSV) and cell polarization studies is found to be 2:1. A direct methanol fuel cell (DMFC) employing carbon-supported Pt-Pd (2:1) alloy (Pt-Pd/C) catalyst as the cathode catalyst delivers a peak-power density of 115 mW/cm(2) at 70 degrees C as compared to peak-power density of 60 mW/cm(2) obtained with the DMFC employing carbon-supported Pt (Pt/C) catalyst operating under similar conditions. In the literature, DMFCs operating with Pt-TiO2 (2:1)/C and Pt-Au (2:1)/C methanol-tolerant cathodes are reported to exhibit maximum ORR activity among the group of these methanol-tolerant cathodes with varying catalysts compositions. Accordingly, the present study also provides an effective route to design methanol-tolerant-oxygen-reduction catalysts for DMFCs. (C) 2011 The Electrochemical Society. DOI: 10.1149/1.3596542] All rights reserved.

Systematic trends in structural and thermodynamic properties of ternary oxides in the systems Ln-Pd-O (Ln = lanthanide element)

Isothermal sections of the phase diagrams for the systems Ln-Pd-O (Ln = lanthanide element) at 1223 K indicate the presence of two inter-oxide compounds Ln(4)PdO(7) and Ln(2)Pd(2)O(5) for Ln = La, Pr, Nd, Sm, three compounds Ln(4)PdO(7), Ln(2)PdO(4) and Ln(2)Pd(2)O(5) for Ln = Eu, Gd and only one compound of Ln(2)Pd(2)O(5) for Ln = Tb to Ho. The lattice parameters of the compounds Ln(4)PdO(7), Ln(2)PdO(4) and Ln(2)Pd(2)O(5) show systematic nonlinear variation with atomic number. The unit cell volumes decrease with increasing atomic number. The standard Gibbs energies, enthalpies and entropies of formation of the ternary oxides from their component binary oxides (Ln(2)O(3) and PdO) have been measured recently using an advanced version of the solid-state electrochemical cell. The Gibbs energies and enthalpies of formation become less negative with increasing atomic number of Ln. For all the three compounds, the variation in Gibbs energy and enthalpy of formation with atomic number is markedly non-linear. The decrease in stability with atomic number is most pronounced for Ln(2)Pd(2)O(5), followed by Ln(4)PdO(7) and Ln(2)PdO(4). This is probably related to the repulsion between Pd2+ ions on the opposite phases Of O-8 cubes in Ln(2)Pd(2)O(5), and the presence of Ln-filled O-8 cubes that share three faces with each other in Ln4PdO7. The values for entropy of formation of all the ternary oxides from their component binary oxides are relatively small. Although the entropies of formation show some scatter, the average value for Ln = La, Pr, Nd is more negative than the average value for the other lanthanide elements. From this difference, an average value for the structure transformation entropy of Ln(2)O(3) from C-type to A-type is estimated as 0.87 J.mol(-1).K-1. The standard Gibbs energies of formation of these ternary oxides from elements at 1223 K are presented as a function of lanthanide atomic number. By invoking the Neumann-Kopp rule for heat capacity, thermodynamic properties of the inter-oxide compounds at 298.15 K are estimated. (C) 2002 Elsevier Science Ltd. All rights reserved.

Coordination driven self-assembly of metallamacrocycles using ambidentate linkers and self-selection of single linkage isomer

Nicotinate-N-oxide and isonicotinate-N-oxide have been employed to synthesize four heterometallic metallamacrocycles (dppf)(2)Pd-2(nicotinate-N-oxide)(2)](OTf)(2) (1), (dppf)(2)Pt-2(nicotinate-N-oxide)(2)](OTf)(2) (2), (dppf) 2Pd2(isonicotinate-N-oxide)(2)](OTf)(2) (3) and (dppf)(2)Pt-2(isonicotinate-N-oxide)(2)](OTf)(2) (4). The complexes represent the first examples of metallamacrocycles driven by solely Pd(II)/Pt(II)-O coordination using carboxylate-N-oxide donor. All the complexes 1-4 are characterized by IR, UV-Vis, multinuclear NMR spectroscopic and ESI-MS studies. The molecular structures of the complexes 1 and 3 are unambiguously determined by single crystal X-ray diffraction analysis. Despite the possibility of formation of several linkage isomers due to ambidentate nature of the donors, exclusive formation of 2 + 2] self-assembled single isomeric metallamacrocycle in each case is interesting observation. (C) 2011 Elsevier B.V. All rights reserved.

Depalladation of Neutral Monoalkyne- and Dialkyne-Inserted Palladacycles and Alkyne Insertion/Depalladation Reactions of Cationic Palladacycles Derived from N,N `,N `'-Triarylguanidines as Facile Routes for Guanidine-Containing Heterocycles/Carbocycles: Synthetic, Structural, and Mechanistic Aspects

Depalladation of the monoalkyne-inserted cyclopalldated guanidines (kappa 2(C,N)Pd(2,6-Me2C5H3N)Br] (I and II) in PhCl under reflux conditions and that of the dialkyne-inserted cyclopalladated guanidine kappa(2)(C,N):eta(2)(C=C)PdBr] (III) in pyridine under reflux conditions afforded a guanidine-containing indole (1), imidaziondole (2), and benzazepine (3) in 80%, 67%, and 76%, yields, respectively. trans-L2PdBr2] species (L = 2,6-Me2C5H3N, C5H5N) were also isolated in the aforementioned reactions in 35%, 42%, and 40% yields. Further , the reaction of the cyclopalladated guanidine kappa(2)(C,N)Pd(mu-Br)](2) (IV) with AgBF4 in a CH2Cl2/MeCN mixture afforded the cationic pincer type cyclopalladated guanidine kappa(3)(C,N,O)Pd(MeCN)]BF4] (4) in 85% yield and this palladacycle upon crystallization in MeCN and the reaction of kappa(2)(C,N)Pd(mu-Br)](2) (V) with AgBf(4) in a CH2Cl2/MeCN mixture afforded the cationic palladacycles {kappa(2)(C,N)Pd(MeCN)(2)]BF4](5 and 6) in 89% and 91% yields, respectively. The separate reactions of 4 with 2 equiv of methyl phenylpropiolate (MPP) or diphenylacetylene (DPA) and the reaction of 5 with 2 equiv of MPP in PhCl at 110 degrees C afforded the guanidine-containing quinazolinium tetrafluoroborate 7 in 25-32% yields. The reaction of 6 with 2 equiv of DPA under otherwise identical conditions afforded the unsymmetrically substituted guanidinium tetrafluoroborate 8, containing a highly substituted naphthalene unit, in 82% yield. Compounds 1-8 were characterized by analytical and spectroscopic techniques, and all compounds except 4 were characterized by single-crystal X-ray diffraction. The Molecular structure of 2 and 3 are nove, as the framework in the former arises due to the formation of two C-N bonds upon depalladation while the butadienyl unit in the latter revealed cis,cis stereochemistry, a-feature unprecedented in alkyne insertion chemistry. Plausible pathways for the formation of heterocycles/carbocycles are proposed. the influence of substitutents on the aryl rings fo the cyclopalladated guanidine moiety and those on alkynes upon the nature of the products in addressed. Heterocycles 1 and 7 revealed the presence of two rotamers in about a 1.00:0.43 ratio in CDCl3 and in about a 1.00:0.14 ratio in CD3OD, respectively, as detected by H-1 NMR spectroscopy while in CD3CN and DMSO-d(6) (1) and CD3CN and CDCl3 (7), these heterocycles revealed the presence of a single rotamer. These spectral features are attributed to the restricted C-N single-bond rotation of the CN3 unit of the guanidine moiety, which possibly arises from steric constraint due to the formation of a N-H center dot center dot center dot Cl hydrogen bond with CDCl3 (1) and N-H center dot center dot center dot O and O-D center dot center dot center dot O hydrogen bonds with CD3OD (7).

Electrocatalytic oxidation of 1,2-propanediol on electrodeposited Pd-poly(3,4-ethylenedioxythiophene) nanodendrite films in alkaline medium

Electrochemical deposition of Pd on conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) coated carbon paper electrode results in the formation of a stable dendritic film of Pd. In the absence of the PEDOT under-layer, Pd deposition is smooth and non-dendritic. Both Pd-PEDOT/C and Pd/C electrodes are studied for electrooxidation of 1,2-propanediol (PD) in an alkaline electrolyte. Owing to enhanced surface area and surface defects on dendritic Pd, the Pd-PEDOT/C electrode exhibits greater catalytic activity than the Pd/C electrode. Cyclic voltammetry studies suggest that peak current density increases with an increase in concentrations of PD and NaOH in the electrolyte. Repetitive cyclic voltammetry and amperometry studies indicate that Pd-PEDOT/C electrode possesses a high electrochemical stability with greater catalytic activity than Pd/C electrode toward electrooxidation of PD. (C) 2012 Elsevier Ltd. All rights reserved.

Insertion Reactions of Six-Membered Cyclopalladated N,N `,N `'-Triarylguanidine, Pd{kappa(2)(C,N)-C6H3Me-3(NHC(NHAr)(=NAr))-2)(mu-Br)](2) (Ar=2-MeC6H4) with PhCC C-C(O)OR (R = Me and Et): A Gateway to Second Orthopalladation through Novel Rearrangements

The reaction of Pd{kappa(2)(C,N)-C6H3Me-3-(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (Ar = 2-MeC6H4; 1) with 4 equiv of PhC C-C(O)OMe in CH2Cl2 afforded Pd{kappa(2)(C,N)-C(Ph)=C(C(O)OMe)C(Ph)=C(C(O)-OMe)C6H3Me-3(N=C(NH Ar)(2))-2}Br] (Ar = 2-MeC6H4; 2) in 70% yield, and the aforementioned reaction carried out with 10 equiv of PhC C-C(O)OR (R = Me, and Et) afforded an admixture of two regioisomers of Pd{kappa(3)(N,C,O)-O=C(OR)-C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)( 2))- 2}Br] (Ar = 2-MeC6H4; R = Me (3a/3b), Et (4a/4b)) in 80 and 87% yields, respectively. In one attempt, the minor regioisomer, 4b, was isolated from the mixture in 6% yield by fractional crystallization. Palladacycles 3a/3b and 4a/4b, upon stirring in CH2Cl2/MeCN (1/1, v/v) mixture at ambient condition for S days, afforded Pd{eta(3)-allyl,(KN)-N-1)-C-5(C(O)OR)(2)Ph3C-(C(O)OR)C6H3Me-3(N=C(NH Ar)(2))(-2)}Br] (Ar = 2-MeC6H4; R = Me (5a/5b), Et (6a/6b)) in 94 and 93% yields, respectively. Palladacycles 3a/3b and 4a/4b, upon reaction with AgOTf in CH2CH2/Me2C(O) (1/1, v/v) mixture at ambient temperature for 15 min, afforded Pd{kappa(3)(N,C,O)-O=C(OR)C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)(2 ))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (7a/7b), Et (8a/8b)) in 79 and 77% yields, respectively. Palladacycles 7a/7b and 8a/ 8b, upon reflux in PhC1 separately for 6 h, or palladacycles 5a/5b and 6a/6b, upon treatment with AgOTf in CH2Cl2/Me2C(O) (7/3, v/v) mixture for 15 min, afforded Pd{(eta(2)-Ph)C5Ph2(C(O)OR)kappa(2)(C,N)-C(C(O)OR)C6H3Me-3(N=C(NHAr) (2))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (9a/9h), Et (10a/10b)) in >= 87% yields. Palladacycles 9a/9b, upon stirring in MeCN in the presence of excess NaOAc followed by crystallization of the reaction mixture in the same solvent, afforded Pd{kappa(3)(N,C,C)-(C6H4)C5Ph2(C(O)OMe)(2)C(C(O)OMe)(2)C6H3Me-3(N=C( NHAr)(2))-2}(NCMe)] (Ar = 2-MeC6H4; 11a/11b) in 82% yield. The new palladacycles were characterized by analytical, IR, and NMR (H-1 and C-13) spectroscopic techniques, and the molecular structures of 2, 3a, 4a, 4b, 5a, 6a, 7a, 9a, 10a, and 11a-d(3) were determined by single crystal X-ray diffraction. The frameworks in the aforementioned palladacycles, except that present in 2, are unprecedented. Plausible pathways for the formation of new palladacycles and the influence of the guanidine unit in 1, substituents in alkynes, reaction conditions, and electrophilicity of the bromide and the triflate upon the frameworks of the insertion products have been discussed.

Self-Assembled Pd(II) Metallocycles Using an Ambidentate Donor and the Study of Square-Triangle Equilibria

The self-assembly reaction of a cis-blocked 90° square planar metal acceptor with a symmetrical linear flexible linker is expected to yield a [4 + 4] self-assembled square, a [3 + 3] assembled triangle, or a mixture of these.However, if the ligand is a nonsymmetrical ambidentate, it is expected to form a complex mixture comprising several linkage isomeric squares and triangles as a result of different connectivities of the ambidentate linker. We report instead that the reaction of a 90° acceptor cis-(dppf)Pd(OTf)2 [where dppf ) 1,1′-bis(diphenylphosphino)- ferrocene] with an equimolar amount of the ambidentate unsymmetrical ligand Na-isonicotinate unexpectedly yields a mixture of symmetrical triangles and squares in the solution. An analogous reaction using cis-(tmen)Pd(NO3)2 instead of cis-(dppf)Pd(OTf)2 also produced a mixture of symmetrical triangles and squares in the solution. In both cases the square was isolated as the sole product in the solid state, which was characterized by a single crystal structure analysis. The equilibrium between the triangle and the square in the solution is governed by the enthalpic and entropic contributions. The former parameter favors the formation of the square due to less strain in the structure whereas the latter one favors the formation of triangles due to the formation of more triangles from the same number of starting linkers. The effects of temperature and concentration on the equilibria have been studied by NMR techniques. This represents the first report on the study of square-triangle equilibria obtained using a nonsymmetric ambidentate linker. Detail NMR spectroscopy along with the ESI-mass spectrometry unambiguously identified the components in the mixture while the X-ray structure analysis determined the solid-state structure.