Group IB organometallic chemistry : XXXVII. Complex forming reactions of polynuclear arylcopper compounds: CalkP bond cleavage in 1,2-bis(diphenylphosphino)ethane (diphos) by (2-Me2NCH2C6H4)4Cu4 and crystal structure of [(C6H5)2PCu · diphos]2 · 2 C6H6

Molecular weight measurements and microwave titrations indicate that no interaction occurs between tetrameric 2-Me₂NCH₂C₆H₄Cu (Ar₄Cu₄) and the monodentate ligands PPh₃, CH₃CN or pyridine. However, the tetrameric structure Ar₄Cu₄ breaks down upon interaction (1/1 molar ratio ArCu/L) with the bidentate ligands (L) Diphos or cis-DPPEE to give the monomeric 1/1 complexes ArCu · L.Addition of Diphos to ArCu · Diphos or conducting the reaction of Ar₄Cu₄ with Diphos in a 1/2 ratio (ArCu/Diphos) gives rise to a C_alkP bond cleavage reaction resulting in the formation of dimeric (Ph₂PCu · Diphos)₂ · 2 C₆H₆, ArH and Ph₂PCHCH₂.The molecular structure of (Ph₂PCu · Diphos)₂ · 2 C₆H₆, has been determined by a single-crystal X-ray diffraction study. Crystals are monoclinic, space group P2₁/c and have Z  2 in a unit cell of dimensions a  12.997(6), b  12.669(7), c  22.839(9) Å and β  94.48(4)°. The structure was refined to R  0.048 for 3048 independent reflections. The four copper atoms in the dimer are held together by two Ph₂P bridges. The bonding in the dimer is discussed.     

Group IB organometallic chemistry: XXXIII. ArAuPPh3, ArAu(CNR), (ArAu)n and Ar4Cu2Au2 compounds in which the aryl group contains 2-MeO, 2,6-(MeO)2, 2-Me2N, 2-Me2NCH2 and (S)- or (R)-2-Me2NCHMe substituents as potential ligands

The synthesis and structural characterization by ¹H NMR and ¹⁹⁷Au Mössbauer spectroscopy as well as by chiral labelling of the built-in ligands of three different types of arylgold(I) compounds is described.¹⁹⁷Au Mössbauer data revealed that the benzyl- and arylgold(I) triphenylphosphine complexes which bear potential coordinating substituents at an ortho position still contain linearly coordinated Au^I with 2c-2e gold(I)carbon bonds. The observation of isochronous NME resonances in (S)-2-Me₂NCH(Me)C₆H₄AuPPh₃ confirms that no additional intramolecular AuN coordination occurs in solution. Preliminary results of an X-ray diffraction study of 2,6-(MeO)₂C₆H₃AuPPh₃ are reported (R = 0.040, PAuC₁ angle 172.6°. Unsymmetrical AuC₁C₂ and AuC₁C₆ angles of 126.4 and 117.4°, respectively).Pure, uncomplexed arylgold(I) compounds have been isolated from the reaction of diarylgoldlithium compounds (arylaurates) with trimethyltin bromide. (S)-2-Me₂NCHMeC₆H₄Au has a dimeric structure which most likely consists of two monomeric units associated by intermolecular AuN coordination thus forming a ten-membered chelate ring. The structure of insoluble 2-Me₂NCH₂C₆H₄Au and 2-Me₂NC₆H₄Au are less clear. The former compound probably has a structure similar to (S)-2-Me₂NCHMeC₆H₄Au (IS/QS values for two-coordinate Au^I centers). However, the strongly deviating IS and QS values of 2-Me₂NC₆H₄Au indicate that a polynuclear structure for this compound similar to that proposed for 2-Me₂NC₆H₄Cu cannot be excluded (a polymeric structure containing 2-Me₂NC₆H₄ groups which span three Au atoms by 3c-2e Au₂C bonds and AuN coordination).The mixed Au/Cu cluster (2-Me₂NCH₂C₆H₄)₄Au₂Cu₂ is accessible via the $\text{1}\text{2}$ reaction of (2-Me₂NCH₂C₆H₄)₄Au₂Li₂ with CuI. Molecular weight and ¹H NMR studies point to a tetranuclear structure in solution, while mass spectrometry shows fragment ions with m/e corresponding to (2-Me₂NCH₂C₆H₄)₃Au₂Cu₂⁺, (2-Me₂NCH₂C₆H₄)₃Cu₂Au⁺, (2-Me₂NCH₂C₆H₄)₂CuAu₂⁺ and of (2-Me₂NCH₂C₆H₄)₂Au⁺.     

Group IB organometallic chemistry : XXXII. Arylcopper compounds ArnCun as intermediates in organometallic synthesis. Single-step synthesis and dynamic NMR spectroscopy of diorganotin dihalides Ar2-nRnSnX2 (Ar  2-Me2NCH2C6H4 or (S)-2-Me2NCHMeC6H4; n  0 or 1)

The selective, single-step synthesis of (2-Me₂NCHZC₆H₄)RSnX₂, in which Z  H or Me, R  Me or Ph and X  Cl or Br, starting from the tetranuclear copper cluster compound (2-Me₂NCHZC₆H₄)₄Cu₄ and RSnX₃ is described. Reaction of (2-Me₂NCH₂C₆H₄)₄Cu₄ with SnBr₄ in a 1/2 molar ratio afforded (2-Me₂NCH₂C₆H₄)₂SnBr₂ in almost quantitative yield.¹H NMR spectroscopic data of these novel compounds, which are monomeric in solution, indicate that: (i) intramolecular SnN coordination renders the Sn atom in (2-Me₂NCHZC₆H₄)RSnX₂ pentacoordinate, with the organo ligands residing in the equatorial plane of a trigonal bipyramidal structure, and the Sn atom in (2-Me₂NCH₂C₆H₄)₂SnBr₂ hexacoordinate, with trans organo groups and a cis arrangement for the Br and the N atoms; (ii) in pyridine the Sn atom in (2-Me₂NCHZC₆H₄)RSnX₂ becomes hexacoordinate by complex formation with the solvent but that intramolecular SnN coordination has been retained.The stereochemical lability of the pentacoordinate Sn center in the diorganotin dihalides (2-Me₂NCHZC₆H₄)RSnX₂, which contain a dissymmetrical equatorial plane, has been established on the basis of the dynamic NMR spectra of     

Group IB organometallic chemistry: XXIX. Synthetic and structural aspects of polynuclear arylcopperlithium compounds Ar4Cu2Li2 (“arylcuprates”) and interaggregate exchange phenomena in Ar4Cu4/Ar4Li4/Ar4Cu2Li2 systems

The thermally stable arylmetal-IB-lithium compounds (2-Me₂NCHZC₆H₄)₄M₂Li₂ (M = Cu, Ag or Au; Z = H or Me) and (2-Me₂NC₆H₄)₄M₂Li₂ have been prepared by a $\text{2}\text{1}$ molar reaction of the aryllithium compounds with the corresponding metal-IB halide (Cu or Ag) or metal-lB halide phosphine complex (BrAuPPh₃). These tetranuclear complexes were also made by an interaggregate exchange reaction of the pure arylmetal-IB clusters with the aryllithium compound.The structure of these compounds in solution consists of aryl groups bridging one metal-lB and one lithium atom of a trans M₂Li₂ core. The four built-in ligands coordinate to lithium resulting in two-coordination at M and four-coordination at Li. These conclusions were based on ¹H and ¹³C NMR spectroscopic data (J(AgC(1)), J(LiC(1)) of solutions of these tetranuclear compounds as well as on the ¹⁹⁷Au Mössbauer data of solid (2-Me₂NC₆H₄)₄Au₂Li₂ (IS 5.65 mm/s and QS 12.01 mm/s).The interaggregate exchange between the tetranuclear species is discussed in terms of an associative mechanism involving formation of an octanuclear intermediate in which the aryl groups can migrate via (3c-2e)edge-(2c-2e)corner(3c-2e)edge movements without M₂Ar bond cleavage.Some aspects of the organic reactions in which organocuprates are involved as intermediates are discussed in terms of the novel structural information.     

Aspects of transmetallation reactions of 2-Me2NCH2C6H4- and 2,6-(Me2NCH2)C6H3-Metal (Pd,Pt, Hg,Tl) complexes with metal carboxylates and low-valent metal (Pd,Pt) complexes

A study has been made of reactions involving organometallic compounds containing ortho-Me₂NCH₂ substituted aryl ligands. The single step syntheses of the new compounds [(2-Me₂NCH₂C₆H₄)₂TlCl], [ [{(S)-2-Me₂NCH(Me)C₆H₄}₂TlCl], [{(S)-2-Me₂NCH(Me)C₆H₄}TlCl₂], [{2,6-(Me₂NCH₂)₂C₆H₃}TlClBr] and [{2,6-(Me₂NCH₂)₂C₆H₃}HgCl] are described. Stable internal NTl coordination at low temperatures has been established for the C-chiral thallium compounds. Reactions of the other Tl and Hg compounds and of [(2-Me₂NCH₂C₆H₄)₂Hg] with Pd(O₂CMe)₂, and also of the reverse reaction of cis-[(2-Me₂NCH₂C₆H₄)₂Pd] with Hg(O₂CR)₂ or Tl(O₂CR)₃, gave transmetallation of one organo ligand and led to a single mono-organopalladium compound and corresponding by-products. Reaction of cis-[(₂-Me₂NCH₂C₆H₄)₂Pd] with Pd(O₂CR)₂ gave the dimeric compound [{(2-Me₂NCH₂C₆H₄)Pd(O₂CR)}₂]. cis-[(2-Me₂NCH₂C₆H₄)₂Pt] did not react with Pd(O₂CMe)₂, while reaction of trans-[(2-Me₂NCH₂C₆H₄)₂Pt] or cis-[(2-Me₂NC₆H₄CH₂)₂Pt] with Pd(O₂CMe)₂ resulted in decomposition. Upon heating, trans-[(2-Me₂NCH₂C₆H₄)₂Pt] was isomerized to cis-isomer. A redox reaction between [(2-Me₂NCH₂C₆H₄)₂Hg] and [Pt(COD)₂] (COD  1,5-cyclo-octadiene) and [Pd₂(DBA)₃] (DBA  dibenzylideneacetone) gave the cis-isomers of [(2-Me₂NCH₂C₆H₄)₂M] (M  Pd, Pt).The results are discussed in terms of influence of internal coordination of the CH₂NMe₂ group. It is concluded that although internal coordination of the CH₂NMe₂ ligand can stabilize metal—carbon bonds it cannot prevent cleavage of such bonds by electrophiles. In this respect, there is no difference in the behaviour of Hg(O₂CR)₂ and Tl(O₂CR)₃. The reactions are influenced by the metal—nitrogen bond strength, which follows the order PtN > PdN > HgN, TlN. The reactivity of Pt compounds is greatly influenced by their structure and type of ligand. It is proposed that cleavege of PdC bonds occurs mainly by a mechanism involving direct electrophilic attack at the carbon centre.     

Synthesis and structure of tris(4-<Emphasis Type="Italic">N,N</Emphasis>-dimethylaminophenyl) antimony(V) dicarboxylates and diaroxides

Tris(4-N,N-dimethylaminophenyl)antimony dicarboxylates (4-Me₂NC₆H₄)₃Sb[OC(O)R]₂ (R = C₆H₄Me-2 (I), C₆H₄Me-4 (II), CH=CHPh (III)), (4-Me₂NC₆H₄)₃Sb[OC(O)C(O)O] (IV), and (4-Me₂NC₆H₄)₃Sb[OC(O)C₆Cl₄C(O)O] (V)) and tris(4-N,N-dimethylaminophenyl)antimony diaroxides (4-Me₂NC₆H₄)₃Sb(OAr)₂ (Ar = Ph (VI), C₆H₂Br₃-2,4,6 (VII), and C₆H₃Me₂-2,6 (VIII)) have been synthesized by the reaction of tris(4-N,N-dimethylaminophenyl)antimony in ether with carboxylic acids or phenols in the presence of hydrogen peroxide. According to X-ray diffraction analysis data, the Sb atoms in compounds I and VII have a distorted trigonal-bipyramidal coordination, and the axial OSbO angles are 175.4(1)° and 177.9(3)°, respectively. The Sb-O bond lengths are 2.133(3) and 2.142(2) Å in compound I and 2.089(5) Å in compound VII.     

Influence of Cl/Br substitution on the stereochemical peculiarities of copper(I) π‐complexes with the 1‐allyl‐2‐amino­pyridinium cation

By using alternating‐current electrochemical synthesis, crystals of the Cu^Iπ‐complexes bis(1‐allyl‐2‐amino­pyridinium) di‐μ‐chloro‐bis­[chloro­copper(I)], (C₈H₁₁N₂)₂[Cu₂Cl₄] or [H₂NC₅H₄NC₃H₅][CuCl₂], and bis(1‐allyl‐2‐amino­pyridinium) di‐μ‐(chloro/bromo)‐bis­[(chloro/bromo)copper(I)], (C₈H₁₁N₂)₂[Cu₂Br_2.2Cl_1.8] or [H₂NC₅H₄NC₃H₅][CuBr_1.10Cl_0.90], have been obtained and structurally investigated. In each of the isostructural (isomorphous) compounds, the distorted tetrahedral Cu environment involves three halide atoms and the C=C bond of the ligand. Both compounds reside on inversion centres, and the dimeric [Cu₂X₄·2H₂NC₅H₄NC₃H₅] units are bonded into a three‐dimensional structure by N—H⋯X hydrogen bonds. The Br content in the terminal X1 position is much higher than that in the bridged X2 site.     

Characterisation of the first authenticated organomercury hydroxide, 4-Me2NC6H4HgOH

4-Me₂NC₆H₄HgOH was prepared from 4-Me₂NC₆H₄HgOAc. Full characterisation showed that it crystallises as discrete molecules, the first example of a true organomercury hydroxide in the solid state. The structures of 4-Me₂NC₆H₄HgOAc and (4-Me₂NC₆H₄)₂Hg are also discussed.     

Synthesis of substituted quinolines by the electrophilic cyclization of n-(2-alkynyl)anilines

A wide variety of substituted quinolines are readily synthesized under mild reaction conditions by the 6-endo-dig electrophilic cyclization of N-(2-alkynyl)anilines by ICl, I₂, Br₂, PhSeBr, and p-O₂NC₆H₄SCl. The reaction affords 3-halogen-, selenium- and sulfur-containing quinolines in moderate to good yields in the presence of various functional groups. Analogous quinolines bearing a hydrogen in the 3-position have been synthesized by the Hg(OTf)₂-catalyzed ring closure of these same alkynylanilines.     

Steric control in the formation of amine or amide complexes from [Mo(No){HB(3,5-Me2C3N2H)3}I2]

The reaction between [Mo(NO){HB(3,5-Me₂C₃N₂H)₃}I₂] and pyrrolidine or piperidine produces both the amine complexes [Mo(NO){HB(3,5-Me₂C₃N₂H)₃} I(NHC_nH₂n)] (n = 4 or 5) and the amide complexes [Mo(NO){HB(3,5-Me₂C₃N₂H)_3} I(NC_nH_2n)]. The role of steric factors in the formation of these compounds is discussed.     

A novel class of aryldiazene complexes: [(PPh3)2 (CO)IrCl(HNNC6H4R-p)(CCPh)] (BF4) (R = NO2, CN,COCH3)

In the reaction with phenylacetylene leading to [(PPh₃)₂(CO)IrCl (HNNC₆H₄R-p)(CCPh)] (BF₄) (R  NO₂, CN, COCH₃), the vacant coordination site in [(PPh₃)₂ (CO)IrCl(N₂C₆H₄ R-p)] (BF₄) plays a key role in the activation of the acetylenic CH bond. ca]To whom correspondence should be addressed.     

Unique Isle Anion [Cu6Cl10]4- in π-Complex of Cu(I) Chloride with 1-(2-Pyridyl)-4-allyl-piperazinium. Synthesis and crystal structure of [(C5H4NH)NC4H8NH(C3H5]2+[Cu3Cl5]2-

Single crystals of [(C₅H₄NH)NC₄H₈NH(C₃H₅)]²⁺[Cu₃Cl₅]^2? are obtained by ac synthesis in ethanol from 1-(2-pyridyl)-4-allyl-piperazinium and Cu(II) dichlorides and their structure is studied by X-ray diffraction analysis (space group P-1, a = 7.246(7) Å, b = 8.54(1) Å, c = 16.41(1) Å, α = 70.76(8)°, β = 77.24(8)°, λ = 80.42(9)°, V = 30(4) ų, Z = 2, R(F) = 0.0686. In the structure of this π-complex, the Cu and Cl atoms form unusual centrosymmetrical Cu₆Cl₁₀ fragments, each fragment being bonded to two 1-(2-pyridyl)-4-allyl-piper-azinium cations via π-interaction Cu-(C=C). A three-dimensional structure is formed by means of N-H…Cl hydrogen bonds. The trigonal-pyramidal surrounding of the Cu(1) atom includes three Cl atoms and the C=C bond, while the tetrahedral surrounding of Cu(2) and the trigonal surrounding of Cu(3) involve the Cl atoms only.     

Group IB organometallic chemistry: XVI. Complex formation between 2-(dimethylamino)-phenylcopper with copper(I) or silver halides. Synthesis and structural characterization of hexanuclear (2-Me2NC6H4)4Cu6-nMnX2 (M = Cu or Ag) cluster compounds

The $\text{2}\text{1}$ complexes (2RCu · MX) between 2-(dimethylamino)phenylcopper (RCu) and CuX (X = Cl, Br or I) or AgBr have been prepared in two ways (i) from the $\text{2}\text{3}$ reaction of 2-(dimethylamino)phenyllithium with cuprous halide and (ii) from the reaction of RCu with excess of the metalIB halide.The structure of bis[(2-dimethylamino)phenylcopper] cuprous bromide, which is dimeric (R₄Cu₆Br₂) in the solid state, has been determined by X-ray analysis. The bonding in this hexanuclear cluster (CuCu ranging from 2.48 to 2.70 Å, multicenter bonded aryl groups) is discussed. Molecular weight determinations and ¹H NMR spectroscopy reveal a similar hexanuclear structure for the R₄Cu₆X₂ complexes in benzene solution. NMR spectroscopy indicates that in solution the mixed-metal cluster compounds R₄Cu_6-nAg_nBr₂ are not stable but enter into interaggregate exchange reactions. A possible pathway involving trinuclear species R₂Cu_3-nAg_nX as intermediates is proposed.     

Preparation of ortho-substituted aryldifluorophosphines, 2-XC6H4PF2 (X = MeO or Me2N), and some of their derivatives. X-ray crystal structure determination of (2-MeOC6H4P)4 and of the platinum complex,Cl2Pt(2-MeOC6H4PF2)2

The preparation of the ortho-substituted aryldifluorophosphines 2-MeOC₆H₄PF₂ and 2-Me₂NC₆H₄PF₂ by chlorine-fluorine exchange from the corresponding dichlorophosphines using sodium fluoride in acetonitrile in the presence of a crown ether is described. The ortho-substituted aryldichlorophosphines 2-MeOC₆H₄PCl₂ and 2-Me₂NC₆H₄PCl₂ were prepared from the respective bis(N,N-dimethylamino) phosphines by cleavage of the PN bonds with hydrogen chloride. The reaction of 4-fluoroanisole and 2-methoxy-phenyllithium with phosphorus trichloride did not yield the expected chlorophosphines, i.e. 2-MeO-5-F-C₆H₃PCl₂ and 2-MeOC₆H₄PCl₂, but led to formation of 4-fluorophenyldichlorophosphite in the former, and to tris(2-methoxyphenyl)phosphine in the latter case. The difluorophosphine 2-MeOC₆H₄PF₂ was found to undergo a spontaneous oxidation-reduction reaction with formation of the tetrafluorophosphorane 2-MeOC₆H₄PF₄, and the cyclotetraphosphine (2-MeOC₆H₄P)₄. A single-crystal X-ray structure determination of the latter indicated the presence of a strongly puckered four-membered ring with PP bond lengths ranging between 222 and 223 pm, and endocyclic bond angles of 84°. Vicinal MeOC₆H₄ groups were found arranged trans to each other. Dichloroplatinum(II) complexes were prepared, involving the two new fluorophosphines, 2-XC₆H₄PF₂ (X = MeO or Me₂N), as ligands. In neither case was any evidence found for coordination between platinum and oxygen or nitrogen, and the fluorophosphines were found to function solely as phosphorus donors. The absence of interaction between platinum and the oxygen atom in the ortho position of the ligand 2-MeOC₆H₄PF₂ was confirmed in a single-crystal X-ray determination of the complex Cl₂(2-MeOC₆H₄PF₂)₂Pt. The compound was found to exist as a planar, cis-coordinated species with PtCl bond lengths between 232 and 234 pm, and a PtP bond length of 218 pm. All compounds were characterized by NMR spectroscopy (¹H, ³¹P and ¹⁹F, where applicable).     

Synthese und Kristallstruktur von (NH4)3Cu4Ho2Br13. Weitere Bromide vom Typ (NH4)3Cu4M2Br13 (M = Dy?Lu,Y) und Rb3Cu4Ho2Br13

Synthesis and Crystal Structure of (NH₄)₃Cu₄Ho₂Br₁₃. Further Bromides of the (NH₄)₃Cu₄M₂Br₁₃ Type (M = Dy? Lu, Y) and on Rb₃Cu₄Ho₂Br₁₃ Single crystals of (NH₄)₃Cu₄Ho₂Br₁₃ were obtained for the first time from the reaction of CuBr with HoBr₃ which was contaminated with NH₄Br: cubic, space group Pn3 , Z = 2, a = 1101.71(5) pm. The crystal structure may be considered as a variant of the fluorite type according to [(HoBr₆)₄][(NH₄)₆(Cu₄Br)₂] ? Ca₄F₈. Pure products can be prepared from the binary halides in glass ampoules at 350°C. The bromides (NH₄)₃Cu₄M₂Br₁₃ (M = Dy? Lu, Y) and Rb₃Cu₄Ho₂Br₁₃ are isotypic with (NH₄)₃Cu₄Ho₂Br₁₃.     

Copper(II) coordination chemistry of 2-methyl-2-(2-pyridyl)-1,3-propan-diol: Syntheses and structures of mono-, di-, and tricopper complexes

Six copper(II) complexes with N,O-donor ligand 2-methyl-2-(2-pyridyl)-1,3-propan-diol (H₂ppdo) were synthesized and characterized. Treatment of CuCl₂ or Cu(OTf)₂ with H₂ppdo led to the formation of bis(H₂ppdo) monomers [Cu(H₂ppdo)₂][CuCl₄] (1) and [Cu(H₂ppdo)₂](OTf)₂ (2), respectively. Both 1 and 2 are comprised of the copper atom coordinated by two ligands in an axially-compressed tetragonal geometry with the pyridyl N atoms in the axial positions and the alcohol O atoms in the equatorial plane. The treatment of 1 or 2 with Et₃N produced copper(II) complexes of varying nuclearity. Treatment of 1 with excess Et₃N generated two binuclear Cu(II) clusters [Cu₂(Hppdo)₂Cl₂] (3) and [Cu₂(Hppdo)₂Cl₂(CH₃OH)₂] (4), where only one alcohol OH group per ligand has been deprotonated, while similar treatment of 2 with excess Et₃N afforded the trimeric copper(II) species [Cu₃(Hppdo)₄](OTf)₂ (5). The structures of 3 and 4 are similar, with alkoxo-O ligand atoms bridging between two square pyramidal copper atoms, and the alcohol-O ligand atoms either coordinating in the axial position in 3, or uncoordinated in 4. Treatment of CuCl₂ with H₂ppdo and Et₃N afforded the trinuclear Cu(II) complex, [Cu₃(Hppdo)₄]Cl₂ (6). Complexes 5 and 6 are made up of one square-planar copper sandwiched between two tetragonally distorted six-coordinate Cu(Hppdo)₂ moieties, where the bridging alkoxo-O atoms link the copper atoms.     

Investigation of Copper Halide:Hydrothermal Syntheses and Characterization of CuBr2(C12H8N2) and Cu3Br3(C12H8N2)2

The reaction of CuBr₂ with 1,10‐phen‐H₂O (1,10‐phen = 1,10‐phenanthroline) gave two compounds: CuBr₂(C₁₂H₈N₂) and Cu₃Br₃(C₁₂H₈N₂)₂. Their structures have been characterized by single‐crystal X‐ray diffraction analysis, elemental analyses, thermogravimetric analyses (TGA) and measurement of variable temperature magnetic susceptibility. Crystal data for CuBr₂(C₁₂‐H₈N₂): monoclinic, space group P2₁/n, a = 0.9977(3) nm, b = 0.65138(14) nm, c = 1.8207(4) nm, β = 91.624(18)°, V = 1.1828(5) nm³, Z = 2. Crystal data for Cu₃Br₃(C₁₂H₈N₂)₂: monoclinic, space group C2/c, a = 1.00167(11) nm, b = 1.4523(4) nm, c = 1.6295(3) nm, β = 94.386(14)°, V = 2.3635(8) nm³, Z = 3.     

Acyl-platinum(II) and -palladium(II) complexes derived from 2-hydroxybenzaldehyde derivatives. X-ray structure of [Pt(OC6H4CO) (P(p-CH3C6H4)3)2]

Platinum(II) and palladium(II) complexes containing chelating acyl ligands have been synthesized from salicylaldehyde, 2-hydroxynaphthaldehyde and 2-hydroxy-3-methoxybenzaldehyde. The platinum(II) complexes [Pt(acyl)L₂], acyl  OC₆H₄CO, OC₁₀H₆CO, O(m-CH₃OC₆H₃CO), L  tertiary phosphine, 1/2 diphenylphosphinoethane, can be isolated with both monodentate and chelating diphosphines, whereas for palladium only the compounds with chelating phosphines are readily obtainable. The reactions of [Pt(OC₆H₄CO)L₂] with HCl afford trans-[PtCl(OHC₆H₄CO)L₂], L  monodentate tertiary phosphine and cis-[PtCl(OHC₆H₄CO)L₂], L2  1,2-bis-diphenylphosphinoethane, in which the metal—carbon bond remains intact. The structure of [Pt(OC₆H₄CO)-(P(p-CH₃C₆H₄)₃)₂] has been determined by X-ray diffraction methods and found to have the expected square planar structure. Some relevant bond lengths and angles are: PtP; 2.271(4) and 2.348(5) Å; PtC; 1.96(2) Å and PtO; 2.07(1) Å; PPtP  101°, CPtO  82°.     

Sulphur substituted organometallic compounds III. Reactions of Ph3SnCH2CH2SC6H4Me-p with some electrophilic reagents

Two distinct types of reactions of electrophiles, EN, with Ph₃SnCH₂CH₂SC₆H₄Me-p (I) have been established. Thus I₂ and HgCl₂ cleave the phenyltin bond: I + EN → Ph₂(N)SnCH₂CH₂SC₆H₄Me-p + PhE (E  I, N  I; E  HgCl, N  Cl) while from the reactions of Br₂ and MeI, as well as of ArSCl, as previously reported, ethylene is evolved: I + EN → Ph₃SnN + CH₂CH₂ + ESC₆H₄Me-p (E  Br, N  Br; E  Me, N  I)     

Two New Modifications of [P(C6H5)4]2[Cu2I4]

Single crystals of two new modifications of [P(C₆H₅)₄]₂[Cu₂I₄] were obtained by reaction of granulated copper with iodine and [P(C₆H₅)₄]I in dry acetone under nitrogen atmosphere. They crystallise monoclinically, space group P2₁/n (No. 14), a = 11.550(6), b = 7.236(2), c = 27.232(13) Å, β = 98.13(3)°, V = 2253(2) ų, and Z = 2 ([P(C₆H₅)₄]₂[Cu₂I₄]-C), and space group Cc (No. 9), a = 17.133(5), b = 15.941(5), c = 18.762 (6) Å, β = 114.02(1)°, V = 4681(3) ų, and Z = 4 ([P(C₆H₅)₄]₂[Cu₂I₄]-D), respectively. In these compounds the [CuI₂]^? anions form dimers di-μ-iodo-diiodocuprate(I), which are either planar ( C ) or folded ( D ).