Hypercoordinated compounds of gold(I)

Mono- and binuclear gold(I) derivatives ofortho-substituted diphenyl ether, C₆H₅OC₆H₄AuPPh₃ and O(C₆H₄)₂(AuPPh₃)₂, were prepared by the reaction of the 2,2'-dilithium derivative of diphenyl ether with ClAuPPh₃. X-Ray structural study has shown that these compounds contain secondary intramolecular bonds between the gold and oxygen atoms. The interaction of C₆H₅OC₆H₄AuPPh₃ with (AuPPh₃)BF₄ affords the [C₆H₅OC₆H₄(AuPPh₃)₂]BF₄ cationic complex. The latter reacts with PPh₃ to give the starting C₆H₅OC₆H₄AuPPh₃ complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 729–736, April, 1994.The authors wish to thank A. L. Blyumenfel'd for recording³¹P NMR spectra, D. V. Zagorevskii and K. V. Kazakov who obtained mass spectra, and Yu.L. Slovokhotov who carried out the EXSAFS study.The study described in the present paper was partly supported by the International Scientific Fund, grant N Ch. 002479.     

Hypercoordinated gold (i) compounds

The reaction of [O(AuPPh₃)₃]⁺BF₄ ⁻ with a Li, K derivative ofo-cresol followed by the interaction of the reaction product with CO₂ gave (triphenylphosphine)gold acetate. The reaction of ClAuPPh₃ witho-LiC₆H₄SLi afforded (triphenylphosphine)gold thiophenoxide. According to the data of X-ray structural analysis, the latter occurs as a dimer formed through an intermolecular secondary Au…Au bond. The reaction of this complex with diazomethane was accompanied by insertion of carbene into the Au−S bond to form a new gold complex, PhSCH₂AuPPh₃. The reactions with PPh₃Au⁺BF₄ ⁻ or HBF₄ yielded a new tetranuclear gold thiocluster, {[PhS(AuPPh₃)₂]²⁺(BF₄ ⁻)}₂, which involves Au…Au bonds that differ in strength. The structures of the compounds obtained were established by X-ray structural analysis¹H and³¹P NMR spectroscopy, and FAB mass spectrometry. For Part 4, seeIzv. Akad. Nauk, Ser. Khim., 1997, 2244 [Russ. Chem. Bull., 1997,46 2127 (Engl. Transl)]. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 350–355, February, 1998.     

Hypercoordinated gold(I) compounds

A hypercoordinated 2,2′-diaurated 4-tert-butylbiphenyl derivative, which contains an intramolecular Au...Au secondary bond, was first synthesized by the reaction of 2,2′-dilithio-4-tert-butylbiphenyl with ClAuPPh₃. The structure of the complex was established by X-ray structural analysis,¹H and³¹P NMR spectroscopy, and fast-atom bombardment mass spectrometry. For Part 3, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2244–2247, December, 1997.     

Compounds of hypercoordinated gold(i)

A binuclear organic derivative of gold(i) with diphenylmethane CH₂(C₆H₄)₂(AuPPh₃)₂ has been prepared by the reaction of 2,2-dilithiumdiphenylmethane with ClAuPPh₃. X-ray analysis of this compound revealed a transoid conformation of the molecule with agostic bonds between the gold atoms and methylene hydrogens. The complex was characterized by IR,¹H and³¹P NMR, and mass spectral data.For Report 1 seeRuss. Chem. Bull., 1994,43, 681.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1125–1130, June, 1994.This work was performed with partial financial support from the International Science Foundation (Project No. MDV 000).     

Crystal structure of (5-methylcyclopentadienyl)-(1,5-cyclooctadiene) iridium(I)

XRD is used to determine the structure of Cp′Ir(cod) at a temperature of 150(2) K. Crystallographic data for C₁₄H₁₉Ir are: a = 10.8272(5) ?, b = 9.7746(4) ?, c = 10.9180(5) ?, β = 97.3310(10)°, monoclinic symmetry, space group P2₁/n, V = 1146.02(9) ?³, Z = 4, d _calc= 2.199 g/cm³, R = 0.0246. The structure is molecular, built of neutral molecules. The metal atom coordinates carbon atoms of two cyclic ligands: 5-methylcyclopentadienyl-ion (Cp′) and 1,5-cyclooctadiene (cod). Five Ir-C_Cp′ distances lie in the range of 2.21–2.28 ?; four Ir-C_cod distances differ insignificantly, and their average value is 2.114(13) ?. The C₁₁C₁₂C₁₃C₁₄C₁₅ and C₁C₂C₅C₆ planes of ligand fragments are almost parallel, and the angle between normals is 1.9°. In the crystal, molecules are bonded only by van der Waals interactions; in the structure, the eight shortest Ir...Ir distances are in the range of 5.608–7.257 ?. Original Russian Text Copyright ? 2009 by K. V. Zherikova, N. B. Morozova, and I. A. Baidina __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 591–594, May–June, 2009.     

An unusually strong intramolecular C-H...N hydrogen bond in 3-(α-hydroperfluoroisobutyryl)-2-(α-hydroperfluoroisobutyryl)imino-1,3-thiazolidine

An unusually strong intramolecular C-H...N hydrogen bond with the shortest known H...N distance of 2.00(3) » has been found by X-ray diffraction analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1593–1595, August, 1995.     

Unexpected formation of a dimeric cation-anionic complex of hypercoordinated tin in the reaction of bis[(2-oxopyrrolidino)methyl]tin dichloride with AgBF4

A new cation-anionic complex of hypercoordinated tin, {[L₂Sn(OH)]⁺ BF₄ ^?}₂ (L is a bidentate (2-oxopyrrolidino)methyl C,O-chelating ligand), was obtained by the reaction of L₂SnCl₂ with AgBF₄ and structurally characterized by X-ray diffraction analysis. In crystalline form, the BF₄ ^? anions are bound to the dications through O?H...F hydrogen bonds (the H?F distance is 1.78 Å). The octahedral coordination of the Sn atoms is strongly distorted because of a weak additional interaction with solvate molecules of dioxane (the Sn?O distance is 3.16 Å).     

Synthesis of the monosubstituted arylcyanoxime and its Na,Tl(I) and Ag(I) compounds

Nitrosation of 2-chlorophenyl acetonitrile with t-butylnitrite under basic conditions (Meyer reaction) resulted in a high-yield preparation of the first substituted arylcyanoxime, 2-chlorophenyl(oximino)acetonitrile, H(2Cl–PhCO) (HL). The obtained cyanoxime is readily deprotonated in solution by metal hydroxides or carbonates with the formation of yellow sodium, tetrabutylammonium, thallium(I) and silver(I) derivatives. The crystal structure of the Tl(I) complex was determined. Thallium(I) salt (TlL) crystallizes in the monoclinic space group P2₁ n with a?=?3.8382(7), b?=?11.0065(18), c?=?20.901(4)?Å, and β?=?92.447(3)°, V?=?882.2(3) ų, Z?=?4; T?=?193?K (Mo?Kα radiation). The structure was solved by direct methods to a final R of 0.0689 (wR2?=?0.1650) for I?>?2σ(I). The crystal structure of the complex is a one-dimensional coordination polymer that consists of centrosymmetric [TlL]₂ dimers in which Tl₂O₂ rhombohedra are connected to each other at 90.72°. The crystal structure of TlL is an interesting example of the ruffled metal-organic network composed of Tl–O–Tl–O zigzag chains with close (3.838?Å) intermetallic distances comparable to those in metallic thallium (3.42?Å). The cyanoxime anion bridges metal centers and acts as a tridentate ligand where oxygen atoms of the oxime group bond to three different Tl(I) cations with three different bond lengths.     

Transfer of organic groups to gold using organotin compounds

PhSnMe₃ undergoes transmetallation with [AuCl(EPh₃)] (E = P, As) in refluxing toluene forming [AuPh(EPh₃)] and Me₃SnCl. The analogous ⁿBu derivative does not transmetallate, even under forcing conditions. Similarly, 1-(trimethylstannyl)naphthalene and 1-(trimethylstannyl)-8-iodonaphthalene react with [AuCl(PPh₃)] to give good yields of the corresponding naphthylgold(I) complexes which were spectroscopically and structurally characterised.     

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).     

Syntheses and molecular structures of some phosphine-gold(I) derivatives of 1,3-diynes

The syntheses of several diynylgold(I) phosphine complexes, including Au(CCCCH){P(tol)₃} (1), Au(CCCCSiMe₃)(PR₃) (R = Ph 2-Ph, tol 2-tol), Au(CCCCFc)(PPh₃) (3), {(tol)₃P}Au(CC)_nAu{P(tol)₃} [n = 2 (4), 3 (6), 4 (7)], {(Ph₃P)Au}CCCC{Au[P(tol)₃]} (5), [ppn][Au{CCCCAu[P(tol)₃]}₂] (8), [Au₂(μ-I)(μ-dppm)₂][Au(CCCCSiMe₃)₂] (9), Hg{CCCCAu(PR₃)}₂ (R = Ph 10-Ph, tol 10-tol) and {(triphos)Cu}CCCC{Au[P(tol)₃]} (11) are described. Of these, the X-ray molecular structures of 1, 2-tol, 3, 4 and 9 have been determined.     

Thermal Decomposition of Thallium(I) Bis-oxalatodiaquaindate(III) Monohydrate

Thallium(I) bis-oxalatodiaquaindate(III) monohydrate was obtained by precipitation of indium(III) withoxalic acid from slightly acidic solution in the presence of thallium(I). The complex was subjected to chemical analysis. The thermal decomposition behavior of the complex was studied using TG, DTA and DTG techniques. The solid complex salt and the intermediate product of its thermal decomposition were characterized using IR absorption and X-ray diffraction spectra. Based on data from these physicochemical investigations the structural formula of the complex was proposed as Tl[In (C₂O₄)₂ (H₂O)₂]⋅H₂O. This revised version was published online in August 2006 with corrections to the Cover Date.     

Crystal structure of <Emphasis Type="Italic">tris</Emphasis>(1,10-phenanthroline) iron(II) dinitrate dihydrate

The structure of tris(1,10-phenanthroline)iron(II) dinitrate dihydrate [Fe(phen)₃](NO₃)₂·2H₂O was established by X-ray diffraction analysis. The role of hydrogen bonds in crystal packing is discussed.     

Synthesis, characterization and bromination of bis(phosphinoferrocenyl) gold(I) compounds

Reaction of [(dppf)Au₂Br₂] (3) {dppf = 1,1′-bis(diphenylphosphino)ferrocene} and [(dippf)Au₂Br₂] (4) {dippf = 1,1′-bis(diisopropylphosphino)ferrocene} with excess bromine yields two new complexes [(C₅H₄Br₃)(PR₂)AuBr] (R = Ph, 5; R = i-Pr, 6). Bromination of the free diphosphinoferrocene ligands produces the expected brominated cyclopentenes (C₅H₄Br₃)(PR₂) (R = Ph, 7; R = i-Pr, 8) in good yields; however, these compounds could not be complexed to gold due to reduced basicity of 7 and 8. When the bromination is performed under wet aerobic conditions the oxidized pseudo-centrosymmetric product, [doppf][FeBr₄] (9) {doppf = 1,1′-bis(oxodiphenylphosphino)ferrocene, is formed as the major product. Solid-state structures of 1, 2, 4, 6, and 9 have been established by means of single-crystal X-ray crystallography.     

Preparation,Crystal Structure and Spectroscopic Studies of Mixed valence Compound [(Cp4i Rh)2 (μ‐Cl)3] [Rh(CO)2Cl2]

[(Cp⁴ⁱ Rh)₂(μ‐Cl)₃] [Rh(CO)₂Cl₂] (Cp⁴ⁱ = tetraisopropyl‐cyclopenta‐dienyl) has been prepared and its crystal is in the space group of Pbar with a= 0.9417 (8), b = 1.4806 (3), c = 1.5062 (2) nm, a = 92.980(10), β = 97.42(3), γ = 93.98 (3)°, V = 2.0735(18) nm³ and Z = 2. The crystal structure consists of a cation of [(η⁵‐Cp⁴ⁱ) Rh (III)(μ‐Cl)₃ Rh (III) (η⁵‐Cp⁴ⁱ)]⁺ and an anion of [Rh (I) (CO)₂ Cl₂]. The two bulky tetraisopropylcyclopentadienyl ligands are in the ecliptic conformation with angle of 10.19° between two cyclopentadienyl ring planes.     

Synthesis and Crystal Structure of a Novel Three-dimensional Supramolecular Compound [（AgI3）（4-HBPFA）2（H2O）]

1 INTRODUCTION In recent years, the rational design and synthesisof metal-directed supramolecular frameworks throughintermolecular hydrogen bonds, π-π stacking interac-tion or other weak interactions have received muchattention because of their interesting molecular topo-logies and various potential applications in catalysis,superconductor, magnetism, nonlinear optics, sen-sors and molecular recognition[1～4]. On the otherhand, the attachment of mono- or polypyridyl frag-ments to a ferr…     

Synthesis and properties of novel guanidine bases. N,N′,N″-Tris(3-dimethylaminopropyl)-guanidine

The synthesis of novel N,N′,N″-tris(3-dimethylaminopropyl)-guanidine 1 is described and X-ray structure of its hexafluorophosphate salt measured (1H·PF₆). The hydrogen bonding in protonated 1 and in 1H·PF₆ is also discussed.     

Stable N-heterocyclic carbene derivatives of copper(i) and silver(i) containing radical anion redox active ligands

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Bis(triphenylphosphine)4-fluorobenzaldehyde thiosemicarbazone copper(I): Forcing chelation through oxoanions

This paper reports the synthesis and characterization of six compounds of copper(I), stabilized in its reduced state by two triphenylphosphines, in which 4-fluorobenzaldehyde thiosemicarbazone and N-methylthiosemicarbazone act as chelating through their sulfur and imino nitrogen. The three oxoanions that have been chosen, NO₃⁻, SO₄²⁻ and CH₃COO⁻, play an important role: their oxygens are bad competitors with the imino nitrogen of the thiosemicarbazone moiety and moreover they form strong charge assisted hydrogen bondings that stabilize the neutral form of the ligand. The overall packing is determined by intermolecular phenyl–phenyl van der Waals interactions.