1,2‐Bis­(methylsulfanyl)‐1,2‐dicarba‐closo‐dodecaborane(12)

In the title compound, 1,2‐(SCH₃)₂‐1,2‐closo‐C₂B₁₀H₁₀ or C₄H₁₆B₁₀S₂, the methylsulfanyl groups are bonded to the C atoms of the 1,2‐dicarba‐closo‐dodecaborane cage. The C_cage—C_cage distance is 1.8033 (18) Å and the S—C_cage—C_cage—S torsion angle is 1.07 (13)°. The C_cage—C_cage distance is compared with those in other 1,2‐dicarba‐closo‐dodecaborane derivatives.     

Two isostructural carboranes: 3‐phenyl‐1,2‐dicarba‐closo‐dodecaborane(12) and 1‐phenyl‐1,7‐dicarba‐closo‐dodecaborane(12)

Two phenyl‐substituted carboranes, 3‐phenyl‐1,2‐dicarba‐closo‐dodecaborane(12), C₈H₁₆B₁₀, (I), and 1‐phenyl‐1,7‐dicarba‐closo‐dodecaborane(12), C₈H₁₆B₁₀, (II), were found to be isostructural. Comparison of the bond angles at the ipso‐C atoms of the phenyl substituent for (I) and (II) [117.71 (3) and 118.45 (10)°, respectively] indicates that electron donation of the carborane cage for B‐ and C‐substituted carboranes is different.     

Crystal engineering with heteroboranes. II. 1,2‐Di­carboxy‐1,2‐dicarba‐closo‐dodecaborane(12) ethanol hemisolvate

The title compound, 1,2‐(COOH)₂‐1,2‐closo‐C₂B₁₀H₁₀·0.5C₂H₆O or C₄H₁₂B₁₀O₄·0.5C₂H₆O, forms a tetramer by incorporating ethanol (solvent) mol­ecules through hydrogen bonding. Two eight‐membered rings [graph set R(8)] are formed by hydrogen bonding between two carboxyl­ic acid groups, whereas two ten‐membered rings [R(10)] are formed by hydrogen bonding between two carboxyl­ic acid groups and the OH group of an ethanol mol­ecule (solvent). Two crystallographically independent tetramers are present in the crystal structure.     

Solvent–metal interactions in bis[1,2‐dicarba‐closo‐dodecaboran(12)‐1‐yl]mercury(II) dichloromethane solvate and bis[1,12‐dicarba‐closo‐dodecaboran(12)‐1‐yl]mercury(II) tetrahydrofuran solvate

The title compounds, bis­[1,2‐dicarba‐closo‐dodecaboran(12)‐1‐yl]­mercury(II) di­chloro­methane solvate, [Hg(C₂B₁₀H₁₁)₂]·CH₂Cl₂, (I), and bis­[1,12‐dicarba‐closo‐dodecaboran(12)‐1‐yl]­mercury(II) tetra­hydro­furan solvate, [Hg(C₂B₁₀H₁₁)₂]·C₄H₈O, (II), were prepared in excellent yields using a robust synthetic procedure involving the reaction of HgCl₂ with the appropriate monoli­thiocarborane. X‐Ray analysis of the products revealed strong interactions between the Hg atoms in both complexes and the respective lattice solvent. The distances between the Hg^II centers and the Cl atoms of the dichloromethane solvent molecule in the ortho‐carborane derivative, (I), and the O atom of the tetra­hydro­furan molecule in the para‐carborane complex, (II), are shorter than the sums of the van der Waals radii for Hg and Cl (3.53 Å), and Hg and O (3.13 Å), respectively, indicating moderately strong interactions. There are two crystallographically independent mol­ecules in the asymmetric unit of both compounds, which, in each case, are related by differing relative positions of the cages.     

A three‐dimensional ZnII coordination framework: poly[[μ2‐(E)‐1,2‐bis(pyridin‐4‐yl)ethene][μ4‐(E)‐2,2′‐(diazene‐1,2‐diyl)dibenzoato][μ2‐(E)‐2,2′‐(diazene‐1,2‐diyl)dibenzoato]dizinc(II)]

In the title coordination polymer, [Zn₂(C₁₄H₈N₂O₄)₂(C₁₂H₁₀N₂)]_n, the asymmetric unit contains one Zn^II cation, two halves of 2,2′‐(diazene‐1,2‐diyl)dibenzoate anions (denoted L²⁻) and half of a 1,2‐bis(pyridin‐4‐yl)ethene ligand (denoted bpe). The three ligands lie across crystallographic inversion centres. Each Zn^II centre is four‐coordinated by three O atoms of bridging carboxylate groups from three L²⁻ ligands and by one N atom from a bpe ligand, forming a tetrahedral coordination geometry. Two Zn^II atoms are bridged by two carboxylate groups of L²⁻ ligands, generating a [Zn₂(CO₂)₂] ring. Each loop serves as a fourfold node, which links its four equivalent nodes via the sharing of four L²⁻ ligands to form a two‐dimensional [Zn₂L₄]_n net. These nets are separated by bpe ligands acting as spacers, producing a three‐dimensional framework with a 4⁶6⁴ topology. Powder X‐ray diffraction and solid‐state photoluminescence were also measured.     

Synthesis and characterization of three nickel(ii) carborane complexes containing nido- or closo-carborane diphosphine ligand

Three nickel(II) carborane complexes, [Ni₂(μ-Cl)₂{7,8-(PPh₂)₂-7,8-C₂B₉H₁₀}₂] (1), [Ni{7-(OPPh₂)-8-(PPh₂)-7,8-C₂B₉H₁₀}{7,8-(PPh₂)₂-7,8-C₂B₉H₁₀}] (2) and [NiBr₂{1,2-(PPh₂)₂-1,2-C₂B₁₀H₁₀}] · CH₂Cl₂ (3), have been synthesized by the reactions of 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane with NiCl₂ · 6H₂O or NiBr₂ · 6H₂O in ethanol under different conditions, respectively. For complex 1, it could also be obtained under the solvothermal condition. All the three complexes were characterized by elemental analysis, FT-IR, ¹H and ¹³C NMR spectroscopy and X-ray structure determination. Single crystal analysis shows that the molecular symmetry of complex 1 is centrosymmetric, containing two same structure units - Ni(7,8-(PPh₂)₂-7,8-C₂B₉H₁₀) linked by two bridged-Cl atoms. The central square plane formed by the [Ni₂Cl₂] unit is almost parallel to the two side NiPP planes. For complex 2, the coordination environment of the Ni atom is a seriously distorted square-planar, in which two positions come from the chelating diphosphine ligand [7,8-(PPh₂)₂-7,8-C₂B₉H₁₀]⁻ degraded from the closo species, while the other two are occupied by an unsymmetrical chelating phosphine oxide ligand [7-(OPPh₂)-8-(PPh₂)-7,8-C₂B₉H₁₀]⁻. As for complex 3, the geometry at the Ni atom is a slightly distorted square-planar. The closo carborane diphosphine ligand 1,2-(PPh₂)₂-1,2-C₂B₁₀H₁₀ was coordinated bidentately to the metal ion through the two phosphorus atoms, and the two Br atoms are at cis position which can fulfill the four coordination mode of the metal.     

[1,1,2,2‐(CO)4‐1,2‐μ‐(CO)‐4,11‐(SMe2)2‐closo‐1,2‐Co2B10H8]

The title compound, 1,1,2,2‐tetra­carbonyl‐1,2‐μ‐carbonyl‐4,11‐di­methyl­sulfido‐closo‐1,2‐dicobaltadodecaborane, [Co₂(C₄H₂₀B₁₀S₂)(CO)₅], has a closo 12‐vertex {1,2‐Co₂B₁₀H₈} structure with SMe₂ ligands at the exo‐4‐ and 11‐positions. The cluster displays close structural similarities to the SEt₂ analogue.     

Three isotypic polymeric complexes with rare earth cations,but‐2‐enoate anions and 4,4′‐(ethane‐1,2‐diyl)dipyridine and 4,4′‐(ethene‐1,2‐diyl)dipyridine bridging ligands

Three isotypic rare earth complexes, catena‐poly[[aquabis(but‐2‐enoato‐κ²O,O′)yttrium(III)]‐bis(μ‐but‐2‐enoato)‐κ³O,O′:O;κ³O:O,O′‐[aquabis(but‐2‐enoato‐κ²O,O′)yttrium(III)]‐μ‐4,4′‐(ethane‐1,2‐diyl)dipyridine‐κ²N:N′], [Y₂(C₄H₅O₂)₆(C₁₂H₁₂N₂)(H₂O)₂], the gadolinium(III) analogue, [Gd₂(C₄H₅O₂)₆(C₁₂H₁₂N₂)(H₂O)₂], and the gadolinium(III) analogue with a 4,4′‐(ethene‐1,2‐diyl)dipyridine bridging ligand, [Gd₂(C₄H₅O₂)₆(C₁₂H₁₀N₂)(H₂O)₂], are one‐dimensional coordination polymers made up of centrosymmetric dinuclear [M(but‐2‐enoato)₃(H₂O)]₂ units (M = rare earth), further bridged by centrosymmetric 4,4′‐(ethane‐1,2‐diyl)dipyridine or 4,4′‐(ethene‐1,2‐diyl)dipyridine spacers into sets of chains parallel to the [20] direction. There are intra‐chain and inter‐chain hydrogen bonds in the structures, the former providing cohesion of the linear arrays and the latter promoting the formation of broad planes parallel to (010).     

Poly[diaquabis(μ‐4,4′‐bipyridine‐κ2N:N′)bis(ethane‐1,2‐diol)di‐μ‐sulfato‐dicopper(II)]

The title compound, [Cu₂(SO₄)₂(C₁₀H₈N₂)₂(C₂H₆O₂)₂(H₂O)₂]_n, contains two crystallographically unique Cu^II centres, each lying on a twofold axis and having a slightly distorted octahedral environment. One Cu^II centre is coordinated by two bridging 4,4′‐bipyridine (4,4′‐bipy) ligands, two sulfate anions and two aqua ligands. The second is surrounded by two 4,4′‐bipy N atoms and four O atoms, two from bridging sulfate anions and two from ethane‐1,2‐diol ligands. The sulfate anion bridges adjacent Cu^II centres, leading to the formation of linear ...Cu1–Cu2–Cu1–Cu2... chains. Adjacent chains are further bridged by 4,4′‐bipy ligands, which are also located on the twofold axis, resulting in a two‐dimensional layered polymer. In the crystal structure, extensive O—H...O hydrogen‐bonding interactions between water molecules, ethane‐1,2‐diol molecules and sulfate anions lead to the formation of a three‐dimensional supramolecular network structure.     

cis‐[1,2‐Bis(diisopropylphosphino‐κP)‐1,2‐dicarba‐closo‐dodecaborane]dichloroplatinum(II) dichloromethane hemisolvate

The asymmetric unit of the title complex, [PtCl₂(C₁₄H₃₈B₁₀P₂)]·0.5CH₂Cl₂ or cis‐[PtCl₂{1,2‐(PⁱPr₂)₂‐1,2‐C₂B₁₀H₁₀}]·0.5CH₂Cl₂, contains one disordered solvent mol­ecule and two mol­ecules of the complex, in which each Pt^II atom displays slightly distorted square‐planar coordination geometry. The P atoms connected to the cage C atoms are coordinated to the Pt^II atom. The Pt—P distances vary slightly [2.215 (3) and 2.235 (4) Å] and the Pt—Cl distances are equal [2.348 (3) and 2.353 (5) Å].     

Reaction‐path calculations and crystal structures of 1,1′‐(ethylene‐1,2‐diyl)dipyridinium dichloride dihydrate and 1,1′‐(ethylene‐1,2‐diyl)dipyridinium dibromide

The design of new organic–inorganic hybrid ionic materials is of interest for various applications, particularly in the areas of crystal engineering, supramolecular chemistry and materials science. The monohalogenated intermediates 1‐(2‐chloroethyl)pyridinium chloride, C₅H₅NCH₂CH₂Cl⁺·Cl⁻, (I′), and 1‐(2‐bromoethyl)pyridinium bromide, C₅H₅NCH₂CH₂Br⁺·Br⁻, (II′), and the ionic disubstituted products 1,1′‐(ethylene‐1,2‐diyl)dipyridinium dichloride dihydrate, C₁₂H₁₄N₂²⁺·2Cl⁻·2H₂O, (I), and 1,1′‐(ethylene‐1,2‐diyl)dipyridinium dibromide, C₁₂H₁₄N₂²⁺·2Br⁻, (II), have been isolated as powders from the reactions of pyridine with the appropriate 1,2‐dihaloethanes. The monohalogenated intermediates (I′) and (II′) were characterized by multinuclear NMR spectroscopy, while (I) and (II) were structurally characterized using powder X‐ray diffraction. Both (I) and (II) crystallize with half the empirical formula in the asymmetric unit in the triclinic space group P. The organic 1,1′‐(ethylene‐1,2‐diyl)dipyridinium dications, which display approximate C2h symmetry in both structures, are situated on inversion centres. The components in (I) are linked via intermolecular O—H…Cl, C—H…Cl and C—H…O hydrogen bonds into a three‐dimensional framework, while for (II), they are connected via weak intermolecular C—H…Br hydrogen bonds into one‐dimensional chains in the [110] direction. The nucleophilic substitution reactions of 1,2‐dichloroethane and 1,2‐dibromoethane with pyridine have been investigated by ab initio quantum chemical calculations using the 6–31G** basis. In both cases, the reactions occur in two exothermic stages involving consecutive S_N2 nucleophilic substitutions. The isolation of the monosubstituted intermediate in each case is strong evidence that the second step is not fast relative to the first.     

Reaction of (η5‐C5H5)Fe(CO)2I with Anionic Bidentate Phosphine Ligands PPh2(o‐C6H4NHLi) or PPh2(o‐C6H4OLi)

The o‐substituted hybrid phenylphosphines, PPh₂(o‐C₆H₄NH₂) and PPh₂(o‐C₆H₄OH), could be deprotonated with LDA or n‐BuLi to yield PPh₂(o‐C₆H₄NHLi) and PPh₂(o‐C₆H₄OLi), respectively. When added to a solution of (η⁵‐C₅H₅)Fe(CO)₂I at room temperature, these two lithiated reagents produce a chelated neutral complex 1 (η⁵‐C₅H₅)Fe(CO)[C(O)NH(o‐C₆H₄)PPh₂‐C,P‐η²] for the former and mainly a zwitterionic complex 2 , (η⁵‐C₅H₅)Fe⁺(CO)₂[PPh₂(o‐C₆H₄O^?)] for the latter. Complex 1 could easily be protonated and then decarbonylated to give 4 [(η⁵‐C₅H₅)Fe(CO){NH₂(o‐C₆H₄)PPh₂‐N,P‐η²}⁺]. Complexes 1 and 4‐I have been crystallographically characterized with X‐ray diffraction.     

The exopolyhedral ligand orientation (ELO) in 3‐(nitrato‐κO)‐3,3‐bis(triphenylphosphane‐κP)‐3‐rhoda‐1,2‐dicarba‐closo‐dodecaborane(11) dichloromethane 2.2‐solvate

In the title compound, [Rh(C₂H₁₁B₉)(NO₃)(C₁₈H₁₅P)₂]·2.2CH₂Cl₂, studied as a 2.2‐solvate of what was assumed to be dichloromethane, the nitrate ligand lies cis with respect to both cage C atoms. Accordingly, the compound displays a pronounced preferred exopolyhedral ligand orientation (ELO) which is traced to both the greater trans influence of the cage B over the cage C atoms and the greater trans influence of the triphenylphosphane ligands over the nitrate ligand. The overall molecular architecture therefore agrees with that of a number of similar 3‐L‐3,3‐L′₂‐3,1,2‐closo‐MC₂B₉H₁₁ species in the literature.     

Synthesis,Reactivity and Crystal Structures of the Palladium(II) Complexes with the Pyrimidine Containing Ligand: Crystal Structures of [Pd(PPh3)(η1‐C4H3N2)(η2‐S2CNC4H8)] and [Pd(PPh3)(η1‐C4H3N2)(η2‐Tp)]

Treatment of Pd(PPh₃)₄ with 5‐bromo‐pyrimidine [C₄H₃N₂Br] in dichloromethane at ambient temperature cause the oxidative addition reaction to produce the palladium complex [Pd(PPh₃)₂(η¹‐C₄H₃N₂)(Br)], 1 , by substituting two triphenylphosphine ligands. In acetonitrile solution of 1 in refluxing temperature for 1 day, it do not undergo displacement of the triphenylphosphine ligand to form the dipalladium complex [Pd(PPh₃)Br]₂{μ,η²‐(η¹‐C₄H₃N₂)}₂, or bromide ligand to form chelating pyrimidine complex [Pd(PPh₃)₂(η²‐C₄H₃N₂)]Br. Complex 1 reacted with bidentate ligand, NH₄S₂CNC₄H₈, and tridentate ligand, KTp {Tp = tris(pyrazoyl‐1‐yl)borate}, to obtain the η²‐dithiocarbamate η¹‐pyrimidine complex [Pd(PPh₃)(η¹‐C₄H₃N₂)(η²‐S₂CNC₄H₈)], 4 and η²‐Tp η¹‐pyrimidine complex [Pd(PPh₃)(η¹‐C₄H₃N₂)(η²‐Tp)], 5 , respectively. Complexes 4 and 5 are characterized by X‐ray diffraction analyses.     

Synthesis and crystal structure of three nido 11‐vertex platinaborane clusters

The reaction of [PtCl₂(PPh₃)₂] with closo‐B₁₀H₁₀^2? in ethanol under reflux conditions gave two nido 11‐vertex platinaundecaborane clusters: [(PPh₃)₂PtB₁₀H₁₀‐8,10‐(OEt)₂]·CH₂Cl₂ (1) and [(PPh₃)₂PtB₁₀H₁₁‐11‐OEt]·CH₂Cl₂ (2) . A novel B₁₀H₁₀^2? deboronated nido 11‐vertex diplatinaundecaborane [(µ‐PPh₂)(PPh₃)₂Pt₂B₉H₆‐3,9,11‐(OEt)₃]·CH₂Cl₂ (3) was obtained when the same reaction was carried out under solvothermal conditions. All of these compounds were characterized by infrared spectroscopy, NMR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. Both clusters 1 and 2 have a nido 11‐vertex {PtB₁₀} polyhedral skeleton in which the Pt atom lies in the open PtB₄ face. Each Pt atom connects with four B atoms and two P atoms of the PPh₃ ligands. Cluster 3 has a nido 11‐vertex {Pt₂B₉} polyhedral skeleton in which two Pt atoms sit in neighbouring positions of the open Pt₂B₃ face, bridged by a PPh₂ group. Each Pt atom connects three B atoms and a P atom of the PPh₃ ligand. Copyright © 2005 John Wiley & Sons, Ltd.     

1,2‐Ph2‐9‐I‐1,2‐closo‐C2B10H9

The title compound, 9‐iodo‐1,2‐di­phenyl‐1,2‐dicarba‐closo‐dodecaborane(9), C₁₄H₁₉B₁₀I, has the expected pseudo‐icosahedral cluster geometry, with a cage C—C distance of 1.724 (4) Å, comparable to that in the non‐iodinated parent. However, the twist angles, θ, of the phenyl rings are 2.1 (6) and 27.6 (5)°, the latter being unusually large.     

Structural properties of trans‐cyclohexane‐1,2‐diamine complexes of copper(II) and zinc(II) acesulfamates

The title compounds, trans‐bis(trans‐cyclohexane‐1,2‐diamine)bis(6‐methyl‐2,2,4‐trioxo‐3,4‐dihydro‐1,2,3‐oxathiazin‐3‐ido)copper(II), [Cu(C₄H₄NO₄S)₂(C₆H₁₄N₂)₂], (I), and trans‐diaquabis(cyclohexane‐1,2‐diamine)zinc(II) 6‐methyl‐2,2,4‐trioxo‐3,4‐dihydro‐1,2,3‐oxathiazin‐3‐ide dihydrate, [Zn(C₆H₁₄N₂)₂(H₂O)₂](C₄H₄NO₄S)₂·2H₂O, (II), are two‐dimensional hydrogen‐bonded supramolecular complexes. In (I), the Cu^II ion resides on a centre of symmetry in a neutral complex, in a tetragonally distorted octahedral coordination environment comprising four amine N atoms from cyclohexane‐1,2‐diamine ligands and two N atoms of two acesulfamate ligands. Intermolecular N—H...O and C—H...O hydrogen bonds produce R₂²(12) motif rings which lead to two‐dimensional polymeric networks. In contrast, the Zn^II ion in (II) resides on a centre of symmetry in a complex dication with a less distorted octahedral coordination environment comprising four amine N atoms from cyclohexane‐1,2‐diamine ligands and two O atoms from aqua ligands. In (II), an extensive two‐dimensional network of N—H...O, O—H...O and C—H...O hydrogen bonds includes R₂¹(6) and R₄⁴(16) motif rings.     

Syntheses of Halogenated Polyhedral Phosphaboranes: Crystal Structure of conjuncto‐3,3′‐(closo‐1,2‐P2B4Br3)2

Co‐pyrolysis of B₂Br₄ with PBr₃ at 480 °C gave, in addition to the main product closo‐1,2‐P₂B₄Br₄, conjuncto‐3,3′‐(1,2‐P₂B₄Br₃)₂ ( 1 ) and the twelve‐vertex closo‐1,7‐P₂B₁₀Br₁₀ ( 2 ), both in low yields. X‐ray structure determination for 1 [triclinic, space‐group P1 with a = 7.220(2) Å, b = 7.232(2) Å, c = 8.5839(15) Å, α = 97.213(15)°, β = 96.81(2)°, γ = 94.07(2)° and Z = 1] confirmed that 1 adopts a structure consisting of two symmetrically boron–boron linked distorted octahedra with the bridging boron atoms in the 3,3′‐positions and the phosphorus atoms in the 1,2‐positions. The intercluster 2e/2c B–B bond length is 1.61(3) Å. The shortest boron–boron bond within the cluster framework is 1.68(2) Å located between the boron atoms antipodal to the phosphorus atoms. The icosahedral phosphaborane 2 was characterized by ¹¹B‐¹¹B COSY NMR spectroscopy showing cross peaks indicative for the isomer with the phosphorus atoms in 1,7‐positions. Both the X‐ray data of 1 and the NMR spectroscopic data of 1 and 2 give further evidence for the influence of an antipodal effect of heteroatoms to cross‐cage boron atoms and, vice versa, of an additional shielding of the phosphorus atoms caused by B‐Hal substitution at the boron positions trans to phosphorus.     

Kupferchalkogenid‐Clusterverbindungen mit Brom‐funktionalisierter Ligandenhülle

Five new copper chalcogenide cluster molecules, [Cu₄(S–C₆H₄–Br)₄(PPh₃)₄] ( 1 ), [Cu₂₂Se₆(S–C₆H₄–Br)₁₀(PPh₃)₈] ( 2 ), [Cu₂₈Se₆(S–C₆H₄–Br)₁₆(PPh₃)₈] ( 3 ), [Cu₄₇Se₁₀(S–C₆H₄–Br)₂₁(OAc)₆(PPh₃)₈] ( 4 ) and [Cu₈(S–C₆H₄–Br)₆(S₂C–NMe₂)₂(PPh₃)₄] ( 5 ) have been synthesized and characterized by single‐crystal X‐ray structure analysis. Compounds 1 – 4 were prepared from the reaction of CuOAc, p‐Br–C₆H₄–SSiMe₃ and Se(SiMe₃)₂ in the presence of PPh₃. In a further reaction of 1 with ⁱPrMgCl and (Me₂N–CS₂)₂ cluster 5 was crystallized.     

The Nitrogen‐Assisted Triphenylphosphine Displacement of 3‐Hydroxypyridine and 3‐Aminopyridine Ligands in Palladium(II) Complexes: Crystal Structures of [Pd(PPh3)Br]2{μ,η2‐C5H3N(OH)}2 and [Pd(PPh3)Br]2{μ,η2‐C5H3N(NH2)}2

Treatment of Pd(PPh₃₎₄ with 2‐bromo‐3‐hydroxypyridine [C₅H₃N(OH)Br] and 3‐amino‐2‐bromopyridine [C₅H₃N(NH₂)Br] in dichloromethane at ambient temperature cause the oxidative addition reaction to produce the palladium complex [Pd(PPh₃₎₂{η¹‐C₅H₃N(OH)}(Br)], 2 and [Pd(PPh₃₎₂{η¹‐C₅H₃N(NH₂)}(Br)], 3 , by substituting two triphenylphosphine ligands, respectively. In dichloromethane solution of complexes 2 and 3 at ambient temperature for 3 days, it undergo displacement of the triphenylphosphine ligand to form the dipalladium complexes [Pd(PPh₃)Br]₂{μ,η²‐C₅H₃N(OH)}₂, 4 and [Pd(PPh₃)Br]₂{μ,η²‐C₅H₃N(NH₂)}₂, 5 , in which the two 3‐hydroxypyridine and 3‐aminopyridine ligands coordinated through carbon to one metal center and bridging the other metal through nitrogen atom, respectively. Complexes 4 and 5 are characterized by X‐ray diffraction analyses.