19F NMR study ofcis- andtrans- effects of substituted triphenylphosphine ligands intrans-(4-fluorophenyl)triarylphosphine-tri(4-fluorophenyl)phosphineplatinum 4-fluorothiophenoxides

A number of compounds of the type oftrans-4-FC₆H₄Pt(PAr₃)₂SC₆H₄F-4, where Ar is a substituted phenyl group, have been prepared starting from the corresponding chlorides. By exchange reactions oftrans-4-FC₆H₄Pt[P(C₆H₄F-4)₃]₂SC₆H₄F-4 with the above-mentioned compounds or Ar₃P,trans-4-FC₆H₄Pt[P(C₆H₄F-4)₃][PAr₃]SC₆H₄F-4 have been generated in solution. For the latter compounds, the effect of Ar₃P oncis- andtrans-ligands has been studied by the¹⁹F NMR technique. It has been shown that thecis- andtrans-effects of Ar₃P run parallel and are well described by pK _a values and ionization potentials of the unshared electron pair in Ar₃P, as well as by ⁰ constants of the aryl groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1359–1363, July. 1995.     

Progress in NMR spectroscopy,Volume 11 : edited by J.W. Emsley,J. Feeney and J.R. Sutcliffe,Pergamon Press,Oxford, 1978, vii + 298 pages; $ 40.00 (£ 20)

Protonolysis of the complexes trans-[Pt(PEt₃)₂(R)(Me)] (R = C₆H₅ ; m-MeC₆H₄ ; o-MeC₆H₄ ; m-FC₆H₄ ; p-FC₆H₄ ; m-CF₃C₆H₄ and C₆F₅) by hydrogen chloride in methanol/water ($\text{90}\text{10}$ v/v) selectively cleaves the alkyl group yielding trans-[Pt(PEt₃)₂(R)Cl] and methane. A kinetic study of these reactions suggests that the primary step involves a proton transfer to the carbonmetal σ-bond with release of CH₄ in a three-center transition state.     

19F NMR study of the polarization direction and polarity of tin-hydrogen and tin-transition metal bonds in tris(4-fluorophenyl)stannane and its organometallic derivatives

A series of (4-FC₆H₄)₃SnML _n compounds containing tin-transition metal bonds were synthesized. Based on¹⁹F NMR data for these compounds, (4-FC₆H₄)₃SnSn(C₆H₄F-4)₃, and (4-FC₆H₄)₃SnH, conclusions were drawn concerning the polarization direction and relative polarity of the tin-hydrogen and tin-metal bonds in the above compounds and in the hydrides L _n MH and R₃SnH. It was found that, in the general case, the group electronegativities of the L _n M groups do not vary similarly to the electronegativities of the central metal atoms.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1933–1937, November, 1994.     

Tertiary phosphine induced migratory carbonyl insertion in cyclopentadienyl complexes of iron(II)

Cyclopentadienyldicarbonylmethyliron, [CpFe(CO)₂Me] (1), undergoes migratory carbonyl insertion under the influence of isosteric phosphine ligands P(4-FC₆H₄)₃ and P(4-MeC₆H₄)₃. The products of the reaction, [CpFe(CO)(COMe)P(4-FC₆H₄)₃] (2a) and [CpFe(CO)(COMe)P(4-MeC₆H₄)₃] (2b), were characterised by X-ray crystallography. In both structures, the iron atom adopts a pseudo octahedral coordination geometry. Fe-P bond distances are the same at 2.1932(8) Å in 2a and 2b, respectively. Thus, contrary to what was expected, X-ray data could not be used to quantitatively differentiate between the two phosphine ligands in 2a and 2b. Therefore, additional spectroscopic techniques such as IR and NMR were employed. Similarly, the Fe-C bond lengths of the carbonyl (Fe-CO) and acetyl (Fe-COMe) are 1.748(3) and 1.955(3) in 2a, and 1.744(3) and 1.951(3) Å in 2b, respectively.The migratory carbonyl insertion was studied by NMR, IR, and UV-vis spectroscopies to determine the mechanism and the rate law. Results from NMR spectroscopy show that the formation of the product is accompanied by oxidation of the corresponding phosphine ligand. An increase in the reactivity of migratory carbonyl insertion for P(4-MeC₆H₄)₃ was observed when the solvent was changed from CH₂Cl₂ to MeCN. The kinetic data showed that P(4-MeC₆H₄)₃ reacts faster than P(4-FC₆H₄)₃.     

Chiral “P-N-P” ligands, (C20H12O2)PN(R)PY2 [R = CHMe2, Y = C6H5, OC6H5, OC6H4-4-Me, OC6H4-4-OMe or OC6H4-4-Bu] and their allyl palladium complexes

Chiral “P-N-P” ligands, (C₂₀H₁₂O₂)PN(R)PY₂ [R = CHMe₂, Y = C₆H₅ (1), OC₆H₅ (2), OC₆H₄-4-Me (3), OC₆H₄-4-OMe (4) or OC₆H₄-4-^tBu (5)] bearing the axially chiral 1,1′-binaphthyl-2,2′-dioxy moiety have been synthesised. Palladium allyl chemistry of two of these chiral ligands (1 and 2) has been investigated. The structures of isomeric η³-allyl palladium complexes, (R′ = Me or Ph; Y = C₆H₅ or OC₆H₅) have been elucidated by high field two-dimensional NMR spectroscopy. The solid state structure of [Pd(η³-1,3-Ph₂-C₃H₃){κ²-(racemic)-(C₂₀H₁₂O₂)PN(CHMe₂)PPh₂}](PF₆) has been determined by X-ray crystallography. Preliminary investigations show that the diphosphazanes, 1 and 2 function as efficient auxiliary ligands for catalytic allylic alkylation but give rise to only moderate levels of enantiomeric excess.     

Effect of substituents on electronegativities of Ar3Si and Ar3Sn groups: comparison of the results ofab initio quantum-chemical calculation and19F NMR data for Ar3MQC6H4F-4 compounds

Ab initio calculations of group electronegativities () of Ar₃Si and Ar₃Sn groups containing 13 types ofmeta-, para- and polysubstituted phenyl groups have been performed. Calculated values of (Ar₃Si) and (Ar₃Sn) correlate better with the ⁰ Taft constants than with the Hammett constants, which is indicative of the inductive nature of the effect of aryl groups on electronegativities of Ar₃M groups. Good correlations have been found between¹⁹F chemical shifts and the corresponding values of (Ar₃Si) and (Ar₃Sn) for the Ar₃SiC₆H₄F-4, Ar₃SnC₆H₄F-4, Ar₃SnCH₂C₆H₄F-4, and Ar₃SnSC₆H₄F-4 compounds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1921–1924, October, 1995.The work was supported by the Russian Foundation for Basic Research (Project No. 93-03-05528).     

Synthesis,structure, and properties of organoplatinum(ii) derivatives of diphenyl ether

New mono- and disubstituted organoplatinum(II) derivatives of diphenyl ether,cis-(PhOC₆H₄-o)PtCl(PPh₃)₂ and (o-C₆H₄OC₆H₄-o)Pt(PPh₃)₂, were synthesized by the reaction of 2,2-dilithium diphenyl oxide withcis-Cl₂Pt(PPh₃)₂. Transmetallation of (PhOC₆H₄-o)AuPPh₃ withcis-Cl₂Pt(PPh₃)₂ was studied using³¹P NMR monitoring. This reaction proceeds with the retention of configuration to afford ClAuPPh₃ andcis-(PhOC₆H₄-o)PtCl(PPh₃)₂ under kinetically controlled conditions. The latter complex irreversibly isomerizes into thetrans isomer in the presence of equimolar quantities of ClAuPPh₃, whereas, in the presence of free PPh₃, this isomerization is reversible. The structures of the obtained diphenyl oxide derivatives of platinum were confirmed by³¹P NMR and FAB mass spectrometry. It was established by X-ray structural analysis that in thecis-(PhOC₆H₄-o)PtCl(PPh₃)₂ complex, the Pt atom is in a nearly square-planar coordination, and secondary intramolecular Pt...O interaction occurs.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1814–1820, October, 1994.We would like to thank A. L. Blyumenfel'd and P. V. Petrovskii for recording the 31p NMR spectra, and D. V. Zagorevskii and K. V. Kazakov for measuring the mass spectrometric characteristics.This work was supported by the International Science Foundation (Project No. MDV 000).     

Synthesis and characterization of toluene-3,4-dithiolatoantimony(III) derivatives with some oxygen and/or sulphur donor ligands

Replacement reactions of toluene-3,4-dithiolatoantimony(III) chloride with oxygen and/or sulphur donor ligands like benzoic acid, thiobenzoic acid, thioacetic acid, phenol, thiophenol, sodium salicylate and thio glycolic acid in 1:1 molar ratio as well as disodium oxalate in 2:1 molar ratio in refluxing anhydrous benzene yielded toluene-3,4-dithiolatoantimony(III) mono oxo and/or thio carboxylic or phenolic derivatives of the general formula {R = OOCC₆H₅, SOCC₆H₅, SOCCH₃, OC₆H₅, SC₆H₅, OOCC₆H₄(OH) and SCH₂COOH} and

Full-size image (3K)

These newly synthesized derivatives are yellow and brown solids/liquids and are soluble in common organic solvents like benzene, chloroform, dichloromethane, etc. These derivatives have been characterized by melting point determination, molecular weight determination, elemental analysis (C, H, S and Sb), spectral {UV, IR and NMR (¹H and ¹³C)} and thermal (TGA, DTA and DSC) studies.     

Investigation of Polymerization and Cyclization of Dimethyldiethoxysilane by 29Si NMR and FTIR

Dimethyldiethoxysilane (DMDES) appears to be a very promising modifier to introduce functional groups to a silicate network. The polymerization and cyclization of DMDES under acid-catalyzed conditions (DMDES : Ethanol : water : HCl = 1:4:4:3.68 × 10^–4 in molar ratio) were investigated by high resolution liquid ²⁹Si nuclear magnetic resonance (NMR) and Fourier transform infrared spectrometry (FTIR). Time-dependent NMR and FTIR data illustrate that monomers of (CH₃)₂Si(OC₂H₅)₂, (CH₃)₂Si(OC₂H₅)(OH), and (CH₃)₂Si(OH)₂ reach meta-equilibrium in less than 4 minutes. 3-membered rings ((CH₃)₂SiO)₃ appear about half an hour later and 4-membered rings ((CH₃)₂SiO)₄ an hour later, which continue to be formed over 24 hours. The relative concentrations of monomers, linear structures and cyclic structures suggest a modified model for the kinetics of cyclization, where 4-membered rings are formed by dimer-dimer interactions, as opposed to monomer-trimer interactions previously proposed.     

Cyclopentadienylnickel thiolate complexes: synthesis, molecular structures and electrochemical detection of sulfur dioxide adducts

Simple reactions between Ni(η⁵-C₅H₅)(PR₃)Br and the Schiff-base thiols, 4-HSC₆H₄NC(H)C₄H₂SBr-4^′ (1) and 4-HSC₆H₄NC(H)C₄H₃S (2), or organothiols, HSC₆H₄F-4 and HSC₆H₄NH₂-4, produced cyclopentadienylnickel thiolates of the formulae, Ni(η⁵-C₅H₅)(PR₃)(SC₆H₄NC(H)C₄H₂SBr-4) (3), Ni(η⁵-C₅H₅)(PR₃)(SC₆H₄NC(H)C₄H₃S) (4) or Ni(η⁵-C₅H₅)(PR₃)(SC₆H₄X-4) (R=Ph, X=F (6) or NH₂ (7) and R=Bu, X=F (5) or NH₂ (8)) which were characterized by a combination of analytical techniques. Complexes 3, 6 and 7 were structurally characterized by X-ray crystallography, showing that they possess the familiar trigonal geometry around the nickel center. These complexes react with sulfur dioxide, with 5, 6, 7 and 8 exhibiting substantial differences between the redox potentials of the pre- and post-SO₂ compounds to suggest that these complexes can be developed as potentiometric SO₂ sensors.     

Relationships between Fe NMR, Mössbauer parameters, electrochemical properties and the structures of ferrocenylketimines

A comparative study of the electrochemical properties, ⁵⁷Fe NMR and Mössbauer spectroscopic data of compounds [(η⁵-C₅H₅)Fe{(η⁵-C₅H₄)-C(R¹)N-R²}] {R¹ = H, R² = CH₂-CH₂OH (1a), CH(Me)-CH₂OH (1b), CH₂C₆H₅ (1c), C₆H₄-2Me (1d), C₆H₄-2SMe (1e) or C₆H₄-2OH (1f) and R¹ = C₆H₅, R² = C₆H₄-2Me (2d)} is reported. The X-ray crystal structure of [(η⁵-C₅H₅)Fe{(η⁵-C₅H₄)-CHN-C₆H₄-2OH}] (1f) is also described. Density functional theoretical (DFT) studies of these systems have allowed us to examine the effects induced by the substituents of the “-C(R¹)N-R²” moiety or the aryl rings (in 1d-1f) upon the electronic environment of the iron(II) centre.     

Organo group VB chemistry: Part VI. On the electric dipole moments of some substituted tertiary phenylphosphines, -arsines, -stibines and -bismuthines

The dipole moments of the following series of tertiary substituted aryl-group VB compounds were measured: (a) (C₆H₅)₃M and (XC₆H₄)₃M with M = P, As, Sb, Bi and X = 4-F, 4-Cl, 4-CH₃, 3-F, 3-Cl; and (b) (3-XC₆H₄)_3?n PR_n with R = C₆H₅, 4-FC₆H₄ and X = F, Cl. These experimental molecular moments are discussed as a consistent set of data that allows the calculation, within the framework of the vectorial additive method, of suitable group moments, bond moments and configurational parameters.     

[(η-C6H6)Ru(L)(Cl/N3/CN/CH3CN)] complexes of non-planar pyrazolylmethylpyridine ligands: Formation of helices due to C-H?X (X = Cl, N) interaction

Structural analysis of a previously reported half-sandwich complex having three-legged “piano-stool” geometry [(η⁶-C₆H₆)Ru^II(L¹)Cl][PF₆] (1) (L¹ = 2-(pyrazol-1-ylmethyl)pyridine) is described. Treatment of 1 with (i) Ag(CF₃SO₃) in CH₃CN and (ii) NaN₃ in CH₃OH, and (iii) the reaction between [(η⁶-C₆H₆)Ru(L²)Cl]-[PF₆] (2) (previously reported) and NaCN in C₂H₅OH led to the isolation of [(η⁶-C₆H₆)Ru(L¹)(CH₃CN)][PF₆]₂ (3), [(η⁶-C₆H₆)Ru(L¹)(N₃)][PF₆] (4), and [(η⁶-C₆H₆)Ru(L²)(CN)][PF₆] (5), respectively (L² = 2-(3,5-dimethyl-pyrazol-1-ylmethyl)pyridine). The complex [(η⁶-C₆H₆)Ru(L⁴)Cl][PF₆] (6) with a new ligand (L⁴ = 2-[3-(4-fluorophenyl)pyrazol-1-ylmethyl]pyridine) has also been synthesized. The structures of 3-6 have been elucidated (¹H NMR spectra; CD₃CN). The molecular structures of 1, 4, and 6·C₆H₅CH₃ have been determined. Notably, the crystal-packing in these structures is governed by C-H?X (X = Cl, N) interactions, generating helical architectures.     

Excess Volumetric and Spectroscopic Properties of Mixtures of Some <Emphasis Type="Italic">n</Emphasis>-Alkoxyethanols and of Some Polyethers with 2-Pyrrolidinone and <Emphasis Type="Italic">N</Emphasis>-Methyl-2-Pyrrolidinone at 298.15 K

Excess molar volumes V_m^E for binary liquid mixtures of n-alkoxyethanols or polyethers + 2-pyrrolidinone or N-methyl-2-pyrrolidinone have been measured with a continuous dilution dilatometer at 298.15 K and atmospheric pressure as a function of composition. The alkoxyethanols are diethylene glycol monomethylether, 2-(2-methoxyethoxy) ethanol, CH₃(OC₂H₄)₂OH; diethylene glycol monoethylether, 2-(2-ethoxyethoxy) ethanol, C₂H₅(OC₂H₄)₂OH; and diethylene glycol monobutylether, 2-(2-butoxyethoxy) ethanol, C₄H₉(OC₂H₄)₂OH; whereas the polyethers are diethylene glycol dimethylether, bis(2-methoxyethyl)ether, CH₃(OC₂H₄)₂OCH₃; diethylene glycol diethylether, bis(2-ethoxyethyl)ether, C₂H₅(OC₂H₄)₂OC₂H₅; and diethylene glycol dibutylether, bis(2-butoxyethyl)ether, C₄H₉(OC₂H₄)₂OC₄H₉. In all mixtures the excess molar volumes are negative and symmetric across the entire composition range. The excess volumes are fitted to the Redlich–Kister polynomial equation to obtain the binary coefficients and the standard errors. The experimental results have also been discussed on the basis of IR measurements.     

Formamidines and triazenes as precursors for the preparation of rhenium imido-complexes

Summary The rhenium(V) imido-complexes [Re(NR)Cl₃(PPh₃)₂] have been obtained by heating the rhenium(V) derivative [ReOCl₃(PPh₃)₂] with RNHCHNR R = Ph (1a), p-MeC₆H₄ (1b), p-ClC₆H₄ (1c) andp-FC₆H₄ (1d) in THF under reflux. [Re(NR)Cl₃(PPh₃)₂] (R =p-MeQ₆H₄) has also been obtained by heating the rhenium(III)-triazenido complex [ReCl₂(RN N NR)(PPh₃)₂] in CCl₄ under reflux.     

Phosphine σ-sydnonyl complexes of Ni,Pd, and Pt

3-R"-4-Bromosydnones 1 (R" = Me) and 2 (R" = Ph) react with complexes Ì(PR₃)_n (M = Ni, Pd, Pt) to form mononuclear phosphine -sydnonyl d⁸-complexes of trans-configuration MBr(3-R"-sydnon-4-yl)(PR₃)₂: 3, 4 (Ì = Ni, R" = Ph); 5 (M = Pd, R" = Me); 6a (M = Pd, R" = Ph); 7 (M = Pt, R" = Ph). In the reaction of bromosydnone 2 with Pd(PPh₃)₄, the cis-complex PdBr(3-Ph-sydnon-4-yl)(PPh₃)₂ (6b) is formed initially; 6b rearranges in solution to give trans-complex 6a. On heating in THF, complex 6a is converted into the binuclear [PdBr(3-phenylsydnon-4-yl)(PPh₃)]₂ complex (8). The reaction of 4-chloromercurio-3-phenylsydnone (10) with Ni(PEt₃)₄, Pd(PPh₃)₄, and Pt(PPh₃)₄ gives mononuclear NiCl(3-phenylsydnon-4-yl)(PEt₃)₂ complex (11), binuclear [PdCl(3-phenylsydnon-4-yl) (PPh₃)]₂ complex (14), and cis- and trans-bimetallic PtCl(3-phenylsydnon-4-ylmercurio)(PPh₃)₂ complexes 15a and 15b, respectively. UV irradiation of 15a and 15b in a benzene solution induces redox demercuration to yield the PtCl(3-phenylsydnon-4-ylcarbonyl)(PPh₃)₂ complex (16). In carbonylation of complexes 3, 6, and 7, CO insertion into the M--C bond occurred to form the corresponding acyl derivatives MBr(3-phenylsydnon-4-ylcarbonyl)(PR₃)₂ (17--19).     

N(nPr)4[B5O6(OH)4][B(OH)3]2 and N(nBu)4[B5O6(OH)4][B(OH)3]2: Clathrates with a diamondoid arrangement of hydrogen-bonded pentaborate anions

Single-crystal X-ray structure analyses of N(nPr)₄[B₅O₆(OH)₄][B(OH)₃]₂,1, and N(nBu)₄ [B₅O₆(OH)₄][B(OH)₃]₂,2, reveal that these materials are novel clathrates, the isotypic host structures of which are three-dimensional assemblies of hydrogen-bonded [B₅O₆(OH)₄]^– ionsand B(OH)₃ molecules. The assembly of only the pentaborate anions is a distorted (i.e., along [102] elongated) fourconnected diamond-related network. The N(nPr) ₄ ⁺ and N(nBu) ₄ ⁺ ions are trapped within the complex three-dimensional channel systems of the host frameworks. Both1 and2 crystallize monoclinically with space groupP2₁/c andZ=4. The cell constants are:1:a=13.592(5),b=12.082(2),c=17.355(6) Å, =106.60(2)° (298K);2:a=13.874(3),b=12.585(1),c=17.588(4) Å, =107.04(1)° (238 K). The results obtained by both¹¹B and¹³C MAS NMR spectroscopy are discussed. Thermogravimetric studies under a flowing inert-gas atmosphere suggest that water, stemming from polycondensation of the hydrous borate species, is released from the clathrates at ca. 443 K (1) and 398 K (2) before the decomposition of the organic cations starts at ca. 603 K (1) and 603 K (2).Author for correspondence. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82172 (82 pages).     

New ferrocenylmethylphosphines - Preparation, characterisation and coordination chemistry of PH(CH2Fc)2, P(CH2Fc)3 [Fc = Fe(η-C5H5)(η-C5H4)] and their derivatives

The new ferrocenylmethylphosphines PH(CH₂Fc)₂ (1) [Fc = Fe(η⁵-C₅H₅)(η⁵-C₅H₄)] and P(CH₂Fc)₃ (2) and the phosphonium salt [P(CH₂Fc)₃(CH₂OH)]I (3) were synthesised from P(CH₂OH)₃ and [FcCH₂NMe₃]I. [P(CH₂Fc)(CH₂OH)₃]Cl (4) was obtained from P(CH₂Fc)(CH₂OH)₂, CH₂O and HCl. The new phosphines and phosphonium salts were fully characterised by NMR and IR spectroscopy and MS. [Mo(CO)₆] reacts with 1 to give [Mo(CO)₅{PH(CH₂Fc)₂}] (5) in high yield, but attempts to employ 2 as a ligand failed. The reaction of [P(CH₂Fc)₃(CH₂OH)]I (3) and [PH(CH₂Fc)₃]I (obtained in situ from 3 and Na₂S₂O₅) with [WI₂(CO)₃(NCMe)₂] gave the complex salts [P(CH₂Fc)₃(CH₂OH)][WI₃(CO)₄] (6) and [PH(CH₂Fc)₃][WI₃(CO)₄] (7), respectively. [P(CH₂Fc)₄]I (8) was synthesized from PH₂CH₂Fc and [FcCH₂NMe₃]I. Crystal structures were obtained for 1, 3-8.     

Organometallic chemistry of chiral diphosphazane ligands: Synthesis and structural characterisation

The diphosphazane ligands of the type, (C₂₀H₁₂O₂)PN(R)P(E)Y₂ (R = CHMe₂ or (S)-*CHMePh; E = lone pair or S; Y₂ = O₂C₂₀H₁₂ or Y = OC₆H₅ or OC₆H₄Me-4 or OC₆H₄OMe-4 or OC₆H₄Bu^t-4 or C₆H₅) bearing axially chiral 1,1'-binaphthyl-2,2′-dioxy moiety have been synthesised. The structure and absolute configuration of a diastereomeric palladium complex, [PdCl₂{ηsu2}-((O₂C₂₀H₁₂)PN((S)-*CHMePh)PPh₂] has been determined by X-ray crystallography. The reactions of [CpRu(PPh₃)₂Cl] with various symmetrical and unsymmetrical diphosphazanes of the type, X₂PN(R)PYY′ (R = CHMe₂ or (S)-*CHMePh; X = C₆H₅ or X₂ = O₂C₂₀H₁₂; Y=Y′= C₆H₅ or Y = C₆H₅, Y′ = OC₆H₄Me-4 or OC₆H₃Me₂-3,5 or N₂C₃HMe₂-3,5) yield several diastereomeric neutral or cationic half-sandwich ruthenium complexes which contain a stereogenic metal center. In one case, the absolute configuration of a trichiral ruthenium complex, viz. [Cp*Ruη₂-Ph₂PN((S)-*CHMePh)*PPh (N₂C₃HMe₂-3,5)Cl] is established by X-ray diffraction. The reactions of Ru₃(CO)₁₂ with the diphosphazanes (C₂₀H₁₂O₂)PN(R)PY₂ (R = CHMe₂orMe; Y₂=O₂C₂₀H₁₂or Y= OC₆H₅ or OC₆H₄Me-4 or OC₆H₄OMe-4 or OC₆H₄Bu^t-4 or C₆H₅) yield the triruthenium clusters [Ru₃(CO)₁₀{η-(O₂C₂₀H₁₂)PN(R)PY₂}], in which the diphosphazane ligand bridges two metal centres. Palladium allyl chemistry of some of these chiral ligands has been investigated. The structures of isomeric η³-allyl palladium complexes, [Pd(η³-l,3-R′₂-C₃H₃){η²-(rac)-(0₂C₂₀H₁₂)PN(CHMe₂)PY₂}](PF₆) (R′ = Me or Ph; Y = C₆H₅ or OC₆H₅) have been elucidated by high field two-dimensional NMR spectroscopic and X-ray crystallographic studies.