Coordination and reactivity of white phosphorus and tetraphosphorus trisulphide in the presence of the fragment CpFe(dppe) [dppe = 1,2-bis(diphenylphosphino)ethane]

The reaction of [CpFe(dppe)Cl] (1) [dppe = 1,2-bis(diphenylphosphino)ethane] with one equivalent of P₄ or P₄S₃ in the presence of a chloride scavenger, TlPF₆ or AgOTf (OTf = triflate, OSO₂CF₃), affords the complexes [CpFe(dppe)(η¹-P₄)]PF₆ (2) and [CpFe(dppe)(η¹-P_basal-P₄S₃)]OTf (3) which contain the tetrahedral P₄ and the mixed P₄S₃ cage molecule η¹-bound to the metal. Both P₄ and P₄S₃ yield furthermore the dimetal compounds [{CpFe(dppe)}₂(μ,η^1:1-P₄)](PF₆)₂ (4) and [{CpFe(dppe)}₂(μ,η^1:1-P_apical-P_basal-P₄S₃)](OTf)₂ (5), which contain the tetrahedral P₄ or the mixed-cage P₄S₃ molecule tethering two ruthenium fragments via two phosphorus atoms. All the compounds have been characterized by elemental analyses and NMR measurements. The crystal structure of 4 has been determined by X-ray diffraction methods. The complexes readily react with excess water under mild reaction conditions and the outcoming products have been identified.     

Steric and electronic effects in stabilizing allyl-palladium complexes of “P-N-P” ligands, X2PN(Me)PX2 (X = OC6H5 or OC6H3Me2-2,6)

The chemistry of η³-allyl palladium complexes of the diphosphazane ligands, X₂PN(Me)PX₂ [X = OC₆H₅ (1) or OC₆H₃Me₂-2,6 (2)] has been investigated.The reactions of the phenoxy derivative, (PhO)₂PN(Me)P(OPh)₂ with [Pd(η³-1,3-R′,R″-C₃H₃)(μ-Cl)]₂ (R′ = R″ = H or Me; R′ = H, R″ = Me) give exclusively the palladium dimer, [Pd₂{μ-(PhO)₂PN(Me)P(OPh)₂}₂Cl₂] (3); however, the analogous reaction with [Pd(η³-1,3-R′,R″-C₃H₃)(μ-Cl)]₂ (R′ = R″ = Ph) gives the palladium dimer and the allyl palladium complex [Pd(η³-1,3-R′,R″-C₃H₃)(1)](PF₆) (R′ = R″ = Ph) (4). On the other hand, the 2,6-dimethylphenoxy substituted derivative 2 reacts with (allyl) palladium chloro dimers to give stable allyl palladium complexes, [Pd(η³-1,3-R′,R″-C₃H₃)(2)](PF₆) [R′ = R″ = H (5), Me (7) or Ph (8); R′ = H, R″ = Me (6)].Detailed NMR studies reveal that the complexes 6 and 7 exist as a mixture of isomers in solution; the relatively less favourable isomer, anti-[Pd(η³-1-Me-C₃H₄)(2)](PF₆) (6b) and syn/anti-[Pd(η³-1,3-Me₂-C₃H₃)(2)](PF₆) (7b) are present to the extent of 25% and 40%, respectively. This result can be explained on the basis of the steric congestion around the donor phosphorus atoms in 2. The structures of four complexes (4, 5, 7a and 8) have been determined by X-ray crystallography; only one isomer is observed in the solid state in each case.     

Synthesis and characterization of metal diselenophosphates: M[Se2P(OR)2]2 (M = Pd,Pt; R = Et,Pr, Pr)

The first Pd(II) and Pt(II) complexes incorporating diselenophosphate (dsep) ligands are presented. Treatment of M(II) (M = Pd, Pt) salts with two equivalents of the dsep ligand in CH₂Cl₂ yielded square-planar compounds of the type M[Se₂P(OR)₂]₂ (M = Pd, Pt; R = Et, ⁱPr, ⁿPr) (1a–2c). These complexes were characterized by elemental analysis, multinuclear NMR spectroscopy and X-ray diffraction (1b and 2b). The dsep ligands coordinate to the metal in an approximately isobidentate fashion and form four-membered Se–P–Se–M chelate rings. Structural elucidations indicated that minute differences exist in the M–Se bond distances and these were observed from solution ³¹P NMR studies, which exhibited two sets of satellites arising from one-bond coupling to ⁷⁷Se nuclei. A packing diagram showed a chain-like motif which was composed of square-planar M[Se₂P(OR)₂]₂ units and occurred via non-covalent Se?Se secondary interactions.     

New platinum(II) and palladium(II) quinoline-imine-pyridine, quinoline-imine-thiazole and quinoline-imine-imidazole complexes by metal-assisted condensation reactions

Pt(II) and Pd(II) methyl- and chloro-complexes with the tridentate N-donor ligands ((pyridin-2-yl)methylene)quinolin-8-amine (NNPy), ((pyridin-2-yl)ethylidene)quinolin-8-yl-amine (NNMePy), (phenyl(pyridin-2-yl)methylene)quinolin-8-yl-amine (NNPhPy), ((thiazol-2-yl)methylene)quinolin-8-amine (NNTh) and ((imidazol-4-yl)methylene)quinolin-8-amine (NNImH) were prepared by metal-assisted condensation of 8-aminoquinoline and an ortho-substituted aldehydo- or keto- N-heterocycle. Preliminary reactivity studies involving the coordinated tridentate N-donors, the chloro-ligand and the M-CH₃ bond were carried out, leading to the synthesis of several new complexes. During these studies, the formation of a novel five-coordinate Pt(II) carbonyl-complex was observed.     

Synthesis,Characterization, and Reactivity of Cationic Palladium(II) and Platinum(II) Iodo Complexes Containing a Linear or a Tripodal Aminophosphine. The X‐Ray Crystal Structures of [Pd{HN(CH2CH2PPh2)2}I]I and [Pd3{N(CH2CH2PPh2}3)2I4]I2

The complexes [M(PNHP)I]I (PNHP = bis[2‐(diphenylphosphino)ethyl]amine; M = Pd ( 1 ), Pt ( 2 )) and [M(NP₃)I]I (NP₃ = tris[2‐(diphenylphosphino)ethyl]amine; M = Pd ( 3 ), Pt ( 4 )) were prepared by interaction of the appropriate aminophosphine in CH₂Cl₂ with aqueous solutions containing [MCl₄]^2— salts and NaI in a ratio 1:4. Complexes 2 and 3 form the polynuclear compounds [Pt₂(PNHP)₃]I₄ ( 2a ) and [Pd₃(NP₃)₂I₄]I₂ ( 3a ) in the presence of coordinating solvents such as the mixture CD₃OD/D₂O/DMSO‐d₆ and CH₂Cl₂/CH₃OH, respectively. Complex 1 consists of distorted square‐planar cations [Pd(PNHP)I]⁺ and iodide anions able to establish short N‐H···I interactions of 2.850Å. The aminophosphine adopts a boat conformation and is coordinated to palladium in a tridentate chelating fashion. The crystal structure for cations of 3a reveals the presence of two types of distorted square‐planar Pd^II atoms, PdNP₂I and trans‐PdP₂I₂, NP₃ acting as tridentate chelating and bridging ligand, respectively. On the basis of ³¹P {¹H} NMR data it has been shown that each distorted square‐planar Pt(II) centre of 2a contains one PNHP acting as tridentate chelating ligand with the other aminophosphine bridging the two metals via the P atoms. Complexes 3 and 4 were shown by ³¹P {¹H} NMR to have the metal atom bound to the three P atoms of NP₃ and one iodo ligand. Additions of AcCysSH and GSH to 4 result, by a ring‐opening process, in the formation of [Pt(NP₂PO)(SR)] (RS = Acys ( 4a ), GS ( 4b )) in which the ligand contains a dangling arm phosphine oxide group and the platinum atom achieves the four‐coordination involving the N atom of the aminophosphine. Compounds [Pt₂(PNHP)₃]Cl₄ ( 2a′ , 2a″ ), [PtAu(PNHP)₂I]I₂ ( 2b ), and [Pt(PNHP)(ONO₂)](NO₃) ( 2c ) were detected in some extent in solution by reaction of complex 2 with Au(tdg)Cl (tdg = thiodiglycol), AuI and excess AgNO₃, respectively. While 1 does not react with AuI, complex 3 affords the heterobimetallic complexes PdCu(NP₃)I₃ ( 5 ), PdAg₂(NP₃)I₄ ( 6 ) and PdAu(NP₃)I₃ ( 7 ) by interaction with the appropriate iodide M′I (M′ = Cu, Ag, Au) via a chelate ring‐opening.     

Synthesis and characterization of new platinum(II) phosphinate complexes

The syntheses of platinum(II) complexes of bis(dimethylphosphinylmethylene)amine and bis(aminomethyl)phosphinic acid were investigated. In the case of bis(dimethyl-phosphinylmethylene)amine the reaction with K₂[PtCl₄] yields the potassium amino-trichloroplatinate K[PtCl₃L] (L?=?bis(dimethylphosphinylmethylene)amine), which was characterized by multinuclear (¹H, ¹³C, ³¹P, and ¹⁹⁵Pt) NMR spectroscopy in solution. Bis(aminomethyl)phosphinic acid reacts with K₂[PtCl₄] under strictly controlled pH conditions to give colorless crystals of the cisplatin analog K[PtCl₂L′] (L′?=?bis(aminomethyl)phosphinate). This complex was characterized by multinuclear NMR spectroscopy in solution as well as by single-crystal X-ray diffraction in the solid state. The bis(aminomethyl)phosphinate coordinates to platinum via both amino functions, thus acting as a chelating ligand.     

Synthesis of palladium and platinum donor complexes and study of their participation in self-assembly reactions. X-ray crystal structure of [Pt(C6H4CCC5H4N)2(dppp)] (dppp = 1,3-bis(diphenylphosphino)propane)

Novel square-planar compounds [M(NC₅H₄CCH)₂(dppp)](OTf)₂ (M = Pd (1), Pt (2)), [Pt(CCC₆H₄CN)₂(dppp)] (3) and [Pt(C₆H₄CCC₅H₄N)₂(dppp)] (4) (dppp = 1,3-bis(diphenylphosphino)propane) were prepared and characterised. Their potential as building blocks in the generation of heterobimetallic squares was studied. The reaction of 4 and the ditopic acceptor species [Pd(H₂O)₂(dppf)](OTf)₂ enabled a tetrametallic metallocycle containing two platinum and two palladium atoms to be obtained. The crystal X-ray structure of 4 shows that the Pt?N vectors are nearly perpendicular, and confirm the suitability of the compound to act as a corner unit for the construction of molecular squares.     

Palladium(II) and platinum(II) 2-(methoxycarbonyl)ethylselenolates: Synthesis, spectroscopy, structures and their conversion into metal selenide

A diselenide, (MeOOCCH₂CH₂Se)₂ (1) has been prepared by esterification of (HOOCCH₂CH₂Se)₂ in methanol. The reductive cleavage of Se-Se bond in 1 by NaBH₄ in methanol generates MeOOCCH₂CH₂SeNa. The latter in different stoichiometries reacts with [M₂Cl₂(μ-Cl)₂(PR₃)₂] to give a variety of products of compositions [M₂Cl₂(μ-SeCH₂CH₂COOMe)₂(PR₃)₂] (2); [M₂Cl₂(μ-Cl)(μ-SeCH₂CH₂COOMe)(PR₃)₂] (3); [Pd₂(SeCH₂CH₂COOMe)₂(μ-SeCH₂CH₂COOMe)₂(PR₃)₂] (4);[Pd₃Cl₂(μ-SeCH₂CH₂COOMe)₄(PR₃)₂] (5). Treatment of complexes 2 with [M₂Cl₂(μ-Cl)₂(PR₃)₂] affords complexes 3 in nearly quantitative yield. The formation of various products in these reactions is sensitive to stoichiometric ratio of reactants employed. This enables interconversion of various complexes by manipulating mole ratios of appropriate starting materials. A homoleptic palladium complex, [Pd(SeCH₂CH₂COOMe)₂]₆ (6) was isolated from a reaction between Na₂PdCl₄ and MeOOCCH₂CH₂SeNa. All these complexes have been characterized by elemental analysis, IR, UV-Vis and NMR (¹H, ¹³C, ³¹P, ⁷⁷Se, ¹⁹⁵Pt) spectroscopy. Structures of trans-[Pd₂Cl₂(μ-SeCH₂CH₂COOMe)₂(PPh₃)₂] (2d), [Pt₂Cl₂(μ-Cl)(μ-SeCH₂CH₂COOMe)(PⁿPr₃)₂] (3e), [Pd₃Cl₂(μ-SeCH₂CH₂COOMe)₄(PⁿPr₃)₂] (5) and [Pd(SeCH₂CH₂COOMe)₂]₆ (6) have been established unambiguously by X-ray crystallography. In these complexes, there are bridging selenolate ligands with their uncoordinated ester groups. Compound 6 has a centrosymmetric Pd₆Se₁₂ hexagon in which every two palladium atoms are bridged by selenolate ligands. Thermal behaviour of some complexes has been investigated. Pyrolysis of compound 2b in tributylphosphate at 195 °C gave Pd₁₇Se₁₅ nanoparticles which were characterized by XRD and EDAX.     

Synthesis, characterization, protonation studies and X-ray crystal structure of ReH5(PPh3)2(PTA) (PTA = 1,3,5-triaza-7-phosphaadamantane)

The novel rhenium pentahydride complex [ReH₅(PPh₃)₂(PTA)] (2) was synthesized by dihydrogen replacement from the reaction of [ReH₇(PPh₃)₂] with PTA in refluxing THF. Variable temperature NMR studies indicate that 2 is a classic polyhydride (T_1(min) = 133 ms). This result agrees with the structure of 2, determined by X-ray crystallography at low temperature. The compound shows high conformational rigidity which allows for the investigation of the various hydride-exchanging processes by NMR methods. Reactions of 2 with equimolecular amounts of either HFIP or HBF₄ · Et₂O at 183 K afford [ReH₅(PPh₃)₂{PTA(H)}]⁺ (3) via protonation of one of the nitrogen atoms on the PTA ligand. When 5 equivalents of HBF₄ · Et₂O are used, additional protonation of one hydride ligand takes place to generate the thermally unstable dication [ReH₄(η²-H₂)(PPh₃)₂{PTA(H)}]²⁺ (4), as confirmed by ¹H NMR and T₁ analysis. IR monitoring of the reaction between 2 and CF₃COOD at low temperature shows the formation of the hydrogen bonded complex [ReH₅(PPh₃)₂{PTA?DOC(O)CF₃}] (5) and of the ionic pair [ReH₅(PPh₃)₂{PTA(D)?OC(O)CF₃}] (6) preceding the proton transfer step leading to 3.     

On the Reactivity of the Platina‐β‐diketone [Pt2{(COMe)2H}2(μ‐Cl)2] Towards Ph2PCH2CH2CH2SOxPh (x = 0, 2)

The reaction of the electronically unsaturated platina‐β‐diketone [Pt₂{(COMe)₂H}₂(μ‐Cl)₂] ( 1 ) with Ph₂PCH₂CH₂CH₂SPh ( 2 ) leads selectively to the formation of the acetyl(chlorido) platinum(II) complex (SP‐4‐3)‐[Pt(COMe)Cl(Ph₂PCH₂CH₂CH₂SPh‐κP,κS)] ( 4 ) having the γ‐phosphinofunctionalized propyl phenyl sulfide coordinated in a bidentate fashion (κP,κS). In boiling benzene complex 4 undergoes decarbonylation yielding the methyl(chlorido) platinum(II) complex (SP‐4‐3)‐[PtMeCl(Ph₂PCH₂CH₂CH₂SPh‐κP,κS)] ( 6 ). However, the reaction of 1 with the analogous γ‐diphenylphosphinofunctionalized propyl phenyl sulfone Ph₂PCH₂CH₂CH₂SO₂Ph ( 3 ) affords the acetyl(chlorido) platinum(II) complex (SP‐4‐4)‐[Pt(COMe)Cl(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂] ( 5 ). In boiling benzene complex 5 undergoes a CO extrusion yielding (SP‐4‐4)‐[PtMeCl(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂] ( 8 ) whereas in presence of 1 the formation of the carbonyl complex (SP‐4‐3)‐[PtMeCl(CO)(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)] ( 7 ) is observed. Addition of Ag[BF₄] to complex 5 leads to the formation of the cationic methyl(carbonyl) platinum(II) complex (SP‐4‐1)‐[PtMe(CO)(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂][BF₄] ( 9 ). All complexes were characterized by microanalysis and NMR spectroscopy (¹H, ¹³C, ³¹P) and complexes 4 and 6 additionally by single‐crystal X‐ray diffraction analyses.     

Oxidative addition of (PhSe)2 and (FcSe)2 to zerovalent palladium and platinum trialkylphosphine complexes (Fc = ferrocenyl, [Fe(η-C5H5)(η-C5H4)])

Room temperature reaction of [Pd₂(dba)₃]/PR₃ or [Pt(C₂H₄)(PR₃)₂] (dba = dibenzylideneacetone; R = Et, Bu) with the diselenides (R′Se)₂ (R′ = Ph, Fc) yielded the oxidative addition products trans-[M(SeR′)₂(PR₃)₂] (M = Pd, Pt). These have been characterised by multinuclear NMR and UV-Vis spectroscopy, mass spectrometry, and, in the cases of trans-[Pt(SePh)₂(PR₃)₂] (R = Et, Bu) and trans-[Pt(SeFc)₂(PBu₃)₂], also by X-ray crystallography.     

Formation and structural characterization of mercury complexes from Te(R)CH2SiMe3 (R = Ph, CH2SiMe3) and HgCl2

The reaction of HgCl₂ and Te(R)CH₂SiMe₃ [R = CH₂SiMe₃ (1), Ph (2)] in ethanol yielded a mononuclear complex [HgCl₂{Te(R)CH₂SiMe₃}₂] (R = Ph, 3a; R = CH₂SiMe₃, 3b). The recrystallization of 3a or 3b from CH₂Cl₂ produced a dinuclear complex [Hg₂Cl₂(μ-Cl)₂{Te(R)CH₂SiMe₃}₂] (R = Ph, 4a; R = CH₂SiMe₃, 4b). When 3a was dissolved in CH₂Cl₂, the solvent quickly removed, and the solid recrystallized from EtOH, a stable ionic [HgCl{Te(Ph)CH₂SiMe₃}₃]Cl·2EtOH (5a·2EtOH) was obtained. Crystals of [HgCl₂{Te(CH₂SiMe)₂}]·2HgCl₂·CH₂Cl₂ (6b·2HgCl₂·CH₂Cl₂) were obtained from the CH₂Cl₂ solution of 3b upon prolonged standing. The complex formation was monitored by ¹²⁵Te-, and ¹⁹⁹Hg NMR spectroscopy, and the crystal structures of the complexes were determined by single crystal X-ray crystallography.     

Displacement of neutral nitrogen donors by chloride in [Pt(SNS)(R-py)](ClO4)2 (SNS = 2,6-bis(methylthiomethyl)pyridine; R-py = pyridines): A reactivity comparison between meta- and para-substituted pyridines

The kinetics of the process [Pt(SNS)(R-py)]²⁺ + Cl⁻ → [Pt(SNS)Cl]⁺ + R-py {SNS = 2,6-bis(methylsulfanylmethyl)pyridine; R-py = meta- or para-substituted pyridines covering a wide range of basicity} were studied in methanol at 25 °C. The reactions obey the usual two-term rate law observed in the substitution reactions of square-planar d⁸ complexes. The plots of log k₂ {k₂ = second-order rate constants} against the pK_a of the heterocycles conjugate acids highlighted a different sensitivity of the two groups of N-donors to changes in basicity, thepara-substituted pyridines (4R-py) showing a weaker dependence on pK_a than the meta-substituted (3R-py). The results have been explained on the basis of a π-acidity difference between 3R-py and 4R-py which influences the reaction ground state.     

Synthesis and characterization of Li(I)-M(II) (M = Co, Ni) heterometallic complexes as molecular precursors for LiMO2

Lithium-containing heterometallic complexes with cobalt (Li₂Co₂(Piv)₆(2,4-Lut)₂ (2, Piv is the pivalate anion) and Li₂Co₂(O₂CCH₂Bu^t)₆(2,4-Lut)₂ (3)) and with nickel (Li₂Ni₂(Piv)₆(DME)₂ (4) and Li₂Ni₂(Piv)₆(2,2′-bpy)₂ (5)) were synthesized. The structures of the complexes were established by X-ray diffraction. The magnetic properties of complexes 2 and 4 were studied. The thermal behavior of compounds 2, 3, and 5 was investigated. It was shown that the compounds under study can be used as molecular precursors for the synthesis of lithium cobaltate and nickelate.     

Preparation,NMR studies and crystal structure of mononuclear and dinuclear Pd(II) and Pt(II) complexes that contain 1,2-bis[3-(3,5-dimethyl-1-pyrazolyl)-2-thiapropyl]benzene

The reaction between 1,2-bis[3-(3,5-dimethyl-1-pyrazolyl)-2-thiapropyl]benzene (bddf) and [MCl₂(CH₃CN)₂] (M = Pd(II), Pt(II)) in a 1:1 M/L ratio in CH₂Cl₂ or acetonitrile solution, respectively, gave the complexes trans-[MCl₂(bddf)] (M = Pd(II) (1), Pt(II) (4)), and in a 2:1 M/L ratio led to [M₂Cl₄(bddf)] (M = Pd(II) (2), Pt(II) (5)). Treatment of 1 and 4 with AgBF₄ and NaBPh₄, respectively, gave the compounds [Pd(bddf)](BF₄)₂ (3) and [Pt(bddf)](BPh₄)₂ (6). When complexes 3 and 6 were heated under reflux in a solution of Et₄NBr in CH₂Cl₂/CH₃OH (1:1) for 24 h, analogous complexes to 1 and 4 with bromides instead of chlorides bonded to the metallic centre were obtained. These complexes were characterised by elemental analyses, conductivity measurements, infrared, ¹H, ¹H{¹⁹⁵Pt}, ¹³C{¹H}, ¹⁹⁵Pt{¹H} NMR, HSQC and NOESY spectroscopies. The X-ray crystal structure of the complex [Pd(bddf)](BF₄)₂ · H₂O has been determined. The metal atom is tetracoordinated by the two azine nitrogen atoms of the pyrazole rings and two thioether groups.     

Oxidative addition to dimethylplatinum (II) compounds containing bulky nitrogen ligands: crystal structures of compounds [PtMe3I{(Me2NCH2CH2NCH)Ar}] (Ar = phenanthryl or anthryl)

Oxidative addition of methyl iodide to platinum (II) compounds [PtMe₂{(Me₂NCH₂CH₂NCH)Ar}] (Ar = phenanthryl or anthryl) produced the corresponding platinum (IV) compounds. Processes aimed at reducing the steric crowding at the coordination sphere of the platinum (IV) centre such as C-C restricted rotation of the pendant part of the ligand leading to rotamers and isomerisation of the CN moiety have been detected in solution. The obtained platinum (IV) compounds were characterised by elemental analyses, mass spectrometry and NMR spectroscopy. According to the crystallographic characterisation, the anthracene derivative gave an E conformer while a Z conformation was obtained for the phenanthrene derivative. In order to rationalize the experimental results, DFT calculations have been performed.     

Bimetallic single-source precursors [M(NH3)4][Co(C2O4)2(H2O)2]·2H2O (M = Pd, Pt) for the one run synthesis of CoPd and CoPt magnetic nanoalloys

All the steps of the proposed technique, from the synthesis of single-source precursors to the preparation of CoPd and CoPt nanoalloys, are described. The double complex salts (DCS) [M(NH₃)₄][Co(C₂O₄)₂(H₂O)₂]·2H₂O (M = Pd, Pt), which were synthesized by mixing solutions containing [M(NH₃)₄]²⁺ cations and [Co(C₂O₄)₂(H₂O)₂]²⁻ anions, have been used as precursors. The salts obtained were characterized by IR spectroscopy, thermal analysis, XRD and single crystal X-ray diffraction. The prepared compounds crystallize in the monoclinic (space group I2/m, M = Pd) and orthorhombic (space group I222, M = Pt) crystal systems. Thermal decomposition of the salts in helium or hydrogen atmosphere at 200-600 °C results in the formation of nanoalloys powders (random solid solution Co_0.50Pd_0.50 and chemically ordered CoPt). The size of the bimetallic particles varied from 5 to 20 nm. Order-disorder structural transformations in Co_0.50Pt_0.50 nanoalloys were studied. The magnetic properties of both chemically disordered Co_0.50Pd_0.50 and ordered CoPt clusters have also been measured.     

Six-coordinate organotin(IV) complexes formed using the Kläui ligands; [CpCo{P(OR′)2O}3]SnR3 − nCln

The complexes [CpCo{P(OR′)₂O}₃]SnR_3 − nCl_n [R′ = Me, Et; R = Ph, Me] are readily prepared from the corresponding organotin chloride and the sodium salt of the Kläui ligands. The X-ray crystal structures of the full series are reported for R = Ph, n = 0-3, and these show that they are all six-coordinate, including the Ph₃Sn derivative which is the first example of a SnC₃O₃ coordination sphere. ¹H, ¹³C, ³¹P and ¹¹⁹Sn NMR spectra are reported, and interpreted in terms of significant second-order effects and fluxional processes.