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Treatment of [Fe2(CO)6(μ-S2C3H6)] (1) with triphenylstibine in a 1:1 molar ratio at room temperature in presence of Me3NO resulted compound [Fe2(CO)5(SbPh3)(μ-S2C3H6)] (2) in 88% yield as red crystals. When the reaction was carried out under a 1:5 molar ratio in presence of Me3NO, it resulted a monosubstituted compound [Fe2(CO)5(SbPh3)(μ-S2C3H6)] (2) in 63% yield along with a disubstituted compound [Fe2(CO)4(SbPh3)2(μ-S2C3H6)] (3) in low yield (8%) as red crystals. Reaction of 2 with triphenylstibine in a 1:5 molar ratio under same condition resulted 3 in moderate yield (46%). Compounds 2 and 3 were characterized by elemental analyses, IR, 1H NMR and 13C NMR spectroscopic data. Crystal structures of the compounds were unambiguously determined by single crystal X-Ray diffraction studies. Compound 2 crystalized as monoclinic crystal system with the space group P21/c, a = 9.464(4) A, b = 16.902(7) A, c = 17.081(7) A, β = 101.216(13)° and Z = 4. Compound 3 was triclinic, space group P-1, a = 9.552(3) A, b = 13.985(5) A, c = 16.487(6) A, α = 78.372(16)°, β = 89.976(14)°, γ = 71.638(11)° and Z = 2. Two new diiron propane-1,3-dithiolate complexes, [Fe2(CO)5(SbPh3)(μ-S2C3H6)] (2) and [Fe2(CO)4(SbPh3)2(μ-S2C3H6)] (3), were synthesized by the displacement of carbonyl groups from [Fe2(CO)6(μ-S2C3H6)] (1) with triphenylstibine, and the resulting complexes were structurally characterized. Solid state molecular structure of compound 2 (left) and compound 3 (right)

A series of triphenylarsine and triphenylstibine-stabilized tri-heteroleptic NHC Pd‒allyl complexes were synthesized and characterized. The solid-state structures of the complexes shown mononuclear carbene palladium complexes, in which, each palladium centre was coordinated by an N-heterocyclic carbene, the η3-coordinated allyl moiety and an As or Sb donor. Further investigation of the Pd complexes as catalysts in Sonogashira coupling reaction was carried out and the obtained complexes exhibited good reactivities for aryl bromides.

The oxidative addition of bis-o-benzoquinone Q–(CH=N–N=CH)–Q (L), in which two 3,5-ditert-butyl-o-benzoquinones are linked to each other in positions 6 via the CH=N–N=CH group, to triphenylstibine gave a new binuclear triphenylantimony(V) bis-catecholate complex, Ph3Sb(Cat–(CH=N–N=CH)–Cat)SbPh3 (I). Recrystallization of I from a methanol–trichloromethane mixture resulted in an additional coordination of a methanol molecule to each antimony atom to give the binuclear complex, (CH3OH)Ph3Sb(Cat–(CH=N–N=CH)–Cat)SbPh3(CH3OH) (I · 2CH3OH), the crystals of which (I · 2CH3OH) · 2CH3OH · CHCl3 (II) contain additionally two methanol solvate molecules, which fix the geometry of the nitrogen-containing bridging group, and a trichloromethane molecule. The molecular structure of compound II in the crystalline state was determined by X-ray diffraction (CIF file CCDC no. 1560840).

The synthesis, solid-state structure, and electrochemical behaviour of triphenylstibine-containing Fischer carbene complexes of tungsten(0) of the type [(SbPh3)(CO)4WC(OEt)(Ar)] with Ar = 2-thienyl (1), 2-furyl (2), 2-(N-methyl)pyrrolyl (3) or 2,2′-bithienyl (4) are reported. A density functional theory study of all the possible conformations and isomers of the various moieties in these complexes show that while the 2-furyl group adopts an anti-orientation relative to the ethoxy group, the thienyl and 2-(N-methyl)pyrrolyl adopt a cis-orientation. The preferred orientation of the aryl groups was confirmed by the solid-state structures. An electrochemical study of the complexes reveals that the decreasing order of the metal-centred oxidation and the carbene–carbon reduction of the [(SbPh3)(CO)4WC(OEt)(Ar)] complexes is: Ar = C4H3S > C4H3O > C4H3NMe. The electrochemical study further reveals substitution of a CO group in [(CO)5WC(OEt)(Ar)] with SbPh3, leads to a lowering of the metal-centred oxidation and the carbene–carbon reduction potential of ca. 0.27 and 0.13 V, respectively.

The synthesis and characterization of the first triphenylstibine-containing Fischer carbene complexes of Mo(0) with general formula [(SbPh3)(CO)4MoC(OEt)(Ar)] with Ar = 2-thienyl (1), 2-furyl (2), 2-(N-methyl)pyrrolyl (3), and 2,2′-bithienyl (4) are reported. The solid state crystal structures of these complexes show a syn conformation of the 2-thienyl and 2,2′-bithienyl groups relative to the ethoxy group, and an anti conformation of the 2-furyl group relative to the ethoxy group. Density functional theory calculations using natural bonding orbital (NBO) and quantum theory of atoms in molecules (QTAIM) calculations gave insight into the electronic structure and preferred conformations of these novel complexes. X-ray photoelectron spectroscopy measurements show that the binding energy of the Mo 3d5/2 photoelectron line for the 2-(N-methyl)pyrrolyl-containing Fischer carbene complex, 3, is the smallest; followed by 2 and then 1. This implies that the Mo metal centre is more electron rich in 3, relative to the 2-furyl or 2-thienyl containing Fischer carbene complexes, 2 and 1, respectively.

The electrochemical behaviour of triphenylstibine-containing Fischer carbene complexes of Mo(0) of the type [(SbPh 3 )(CO) 4 MoC(OEt)(Ar)] with Ar = 2-thienyl ( 1 ), 2-furyl ( 2 ), 2-(N-methyl)pyrrolyl ( 3 ) or 2,2'-bithienyl ( 4 ) is reported. Results are compared to the related complexes [(L,L')(CO) 3 MoC(OEt)(Ar)] where L,L' = CO,CO; PPh 3 ,CO; AsPh 3 ,CO; or dppe (1,2-bis(diphenylphosphino)ethane). Linear trends and relationships obtained between HOMO/LUMO energies, oxidation/reduction potentials, ionization energies/electron affinities and X-ray photoelectron spectroscopic binding energies of the Mo 3d 5/2 photoelectron lines, show that the electronic influences of the heteroaryl carbene substituent and pnictogen ligands in Mo(0) Fischer ethoxycarbene complexes are transmitted well through the bonds to the Mo metal centre.

The functionalization of 3,5-di-tert-butylcatechol with a group CH2X in the 6th position (where the group X has the additional heteroatoms) was performed in order to prepare new functionalized 3,5-di-tert-butylcatechols of the common type (6-(CH2-X)-3,5-Cat)H2, where X is methoxy group (catechol 1a, X = OMe), 3,5-dimethylpyrazol-1-yl (catechol 1b, X = Me2Pyr) and benzimidazol-1-yl (catechol 1c, X = Benzimid). The oxidation of catechols 1a-1c with K3[Fe(CN)6] in alkaline medium leads to new functionalized o-quinones 2a-2c and corresponding o-benzoquinones of the type 6-(CH2-X)-3,5-Q. The molecular structures of pyrazolyl-containing catechol 1b and its o-quinone 2b in crystal were determined by single-crystal X-ray analysis. The treatment of o-benzoquinones with triphenylstibine gives new triphenylantimony(V) catecholates (6-(CH2-X)-3,5-Cat)SbPh3 (3a-3c) containing additional functional groups in the substituent at the 6th position of catecholato aromatic ring. The molecular structures of catecholates (6-(CH2-OMe)-3,5-Cat)SbPh3 (3a) and (6-(CH2-Me2Pyr)-3,5-Cat)SbPh3·H2O (3b·H2O) in crystal were determined by means of single-crystal X-ray analysis. In crystal, complex 3a forms two geometrical isomers with different position of CH2OMe group towards aromatic cycle of catecholato ligand. The “CPh–H…π-system” interactions between these isomers were found. The coordination environment of the central antimony atom in 3b·H2O is a distorted octahedral with a coordinated water molecule which is involved in the intramolecular hydrogen bonding with pyrazolyl group of catecholato ligand.

Alkylation of 1,3,5-trimethoxybenzene with 3,5-di-tert-butyl-6-methoxymethylcatechol affords new sterically hindered biscatechol, whose oxidation gives the corresponding bis-o-quinone. Its treatment with triphenylstibine leads to bis-triphenylantimony(v) bis-catecholate.

The new binuclear oxothiolatorhenium(V) compound, Re202(mtp)3 (Dl, mtpH2 = 2mercaptomethylthiophenol) was found to be an efficient catalyst for oxygen-transfer reactions. Electron donor ligands such as phosphines coordinate to one of the rhenium centers in Dl strongly, breaking up one of the Re-S bridges. Dialkylsulfides coordinate weakly. Alkylarj'lsulfides, diarylsulfides, triphenylarsine and triphenylstibine, dienes and alkenes do not coordinate to Di. Dl catalyzes the oxidation of phosphines, arsines, stilbenes, sulfides and dienes by pyridine N-oxides, and the oxidation of phosphines by dimethylsulfoxide. The kinetics and mechanism for the oxidation of triarylphosphines by pyridine N-oxides were investigated. The relative reactivities of all substrates were studied by competitive reactions. The order was found to be: phosphine > arsine > stilbene > sulfide > diene. The reaction is proposed to go through a Re(VII) intermediate with pyridine N-oxide as one of the ligands. The N-O bond was activated through coordination to rhenium and the oxygen atom was abstracted by a phosphine, forming a phosphine oxide. Introduction Oxygen atom transfer reactions are catalyzed by high-valent transition metal-oxo complexes, such as Re^^/Re^,^"^^ Mo^/Mo^,^^'^^ and W^'/W^.Molybdenum and tungsten systems have received the most attention because of their roles in biological systems. In such pairs, the oxidation states differ by two units in keeping with their role as oxotransferases; the metals exist in their highest oxidation states to stabilize the metal-oxo n ^ Reproduced in part with permission from Inorganic Chemistry, submitted for publication. Unpublished work copyright 2000 American Chemical Society.

The structure of dimeric 2,7-bis[4-(trifluoromethyl)phenyl]-4λ4,5λ4,9λ4,10λ4-tetrathieto[1,2-a:3,4-a′]bis [1,2,3,5]dithiadiazole (C8H4F3N2S2)2 and its adduct with triphenylstibine, (C8H4F3N2S2)2·C18H15Sb, both have triclinic (P) symmetry. They crystallize in layers containing centrosymmetric clusters consisting of four dithiadiazolyl dimers in the parent compound and two such dimers paired with two triphenylstibine units in the aromatic co-crystal. In the co-crystal, the Ph3Sb molecules associate with an equivalent moiety from a neighbouring cluster in a geometry that is very reminiscent of other Ph3Sb-containing structures. Thus, the adduct combines structural elements from those of its component parts. Key interactions between molecules in the pure dithiadiazolyl (S to S) and the co-crystal (S to C) are significantly shorter than the sums of atom van der Waals radii.

The synthesis of a stable hydride triphenylstibine derivative, Nb(η5-C5H4SiMe3)2(H)(SbPh3) (1), has been achieved through the formation of the transient coordinatively unsaturated 16-electron speci...

Direct reaction of copper(I) halides with triphenylstibine (tpSb) and 2-mercapto-thiazolidine (tzdtH) in 1:1:1 molar ratio, results in the formation of the [CuX(μ2-S)-tzdtH)(tpSb)]2 (X=Cl (1), Br (2) and I (3)) complexes. The complexes have been characterized by melting point, FT-IR, UV-vis, (1)H NMR spectroscopic data and X-ray crystallography. Complexes 1-3 are di-nuclear and they are the first examples of mixed metals (CuSb), mixed ligand (thioamide, stibine and halogen) containing complexes. Two μ2-S (1-3) atoms bridge the two copper(I) ions with tetrahedral geometry. The coordination sphere around copper atoms is completed by one Sb from tpSb and one halogen (chlorine, bromine or iodine) atom. Intermolecular via N-H⋯X (Cl (1) and Br (2)) interactions stabilized the assembly. The short coppercopper bond distances of 3.103 (1), 3.061 (2) and 3.110, 3.108 (3) Ǻ found in 1-3 indicates d(10)-d(10) interaction between metal centers. The complexes exhibit high photo-sensitivity to UVB light. The complexes 1-3 and the already known [Cu(μ2-I)(tpSb)2]2 (4) were tested for their in vitro cytotoxic activity against human cancer cell lines: MCF-7 (breast, estrogen receptor (ER) positive), MDA-MB-231 (breast, estrogen receptor (ER) negative) and MRC-5 (normal human fetal lung fibroblast cells) with sulforhodamine B (SRB) colorimetric assay. Since estrogen receptors (ERs) are located in MCF-7, in contrast to MDA-MB-231 cells, the estrogenic effect of 1-4 on MCF-7 cells was studied by the mean of methylene blue assay. Compound 4 exhibits the highest estrogenic effect. None of 1-4 exceeds the activity of cisplatin against MCF-7 cells, but they are more active than cisplatin towards MDA-MB-231 cells. UVB light increases the effectiveness of complexes on MCF-7 cells which in the case of 4 is up to 28% higher than the corresponding initial complex (without irradiation).

Platinum complexes [Ph3PhCH2P]+[(Me2S=O)PtCl3]−I and cis-Cl2(Ph3Sb)(Me2S=O)Pt II were synthesized by reaction of triphenylbenzylphosphonium and tetraphenylstibonium chlorides with potassium tetrachloroplatinate in DMSO. Crystal I is formed by triphenylbenzylphosphonium tetrahedral cations [P-CPh 1.791(4)-1.795(4) A, P-CAlk 1.811(4) A; CPC 107.57(18)°-111.46(17)°] and by square anions [(Me2S=O)PtCl3]− [Pt-Cl 2.3236(11), 2.2981(12), 2.2977(11) A; Pt-S 2.1950(10) A; trans-angles SPtCl 177.51(4)°, ClPtCl 178.74(4)°]. In a square-planar complex II [trans-angles SPtCl 178.01(6)°, ClPtSb 177.96(4)°] with central platinum atom the chlorine atoms [Pt-Cl 2.308(1), 2.350(1) A], triphenylstibine [Pt-Sb 2.5118(4) A] and dimethyl sulfoxide [Pt-S 2.195(1) A] molecules are coordinated. Compound II is a first example of mixed ligand complex of platinum(II), where in the coordination sphere of central atom the tertiary stibine is present along with DMSO ligand.

The platinum molecular complex cis-Cl2(Ph3Sb)(Me2S=O)Pt (I) was synthesized by the reaction of tetraphenylstibonium chloride with potassium tetrachloroplatinate in dimethyl sulfoxide. The crystal structure of square-planar complex I was determined by X-ray crystallography. The complex contains, in addition to chlorine atoms, triphenylstibine and DMSO molecules coordinated to the central atom. The bond lengths Pt-Cl, Pt-S, and Pt-Sb are 2.308(1), 2.350(1), 2.195(1), and 2.5118(4) A, respectively. The compound is the first example of mixed-ligand platinum(II) complex in which the coordination sphere of the central atom contains, along with dimethyl sulfoxide ligand, a tertiary stibine ligand.

The complex Re 2 (CO) 8 [μ-η 2 -C(H) C(H)Bu n ](μ-H) ( 1 ) reacts with SbPh 3 at 68 °C to yield the new σ-phenyl dirhenium complex Re 2 (CO) 8 (SbPh 3 )(Ph)(μ-SbPh 2 ) ( 4 ) in 72% yield. Compound 4 contains two rhenium atoms held together by a bridging SbPh 2 ligand. One rhenium atom contains a σ-phenyl group. The other rhenium atom contains a SbPh 3 ligand. Compound 4 was also obtained in 34% yield from the reaction of Re 2 (CO) 10 with SbPh 3 in the presence of UV–Vis irradiation together with some monorhenium products: HRe(CO) 4 SbPh 3 ( 5 ), Re(Ph)(CO) 4 SbPh 3 ( 6 ) and fac -Re(Ph)(CO) 3 (SbPh 3 ) 2 ( 7 ) in low yields. Complex 4 is split by reaction with an additional quantity of SbPh 3 to yield the monorhenium SbPh 3 complexes 6 , 7 and mer -Re(Ph)(CO) 3 (SbPh 3 ) 2 ( 8 ) that contain a σ-phenyl ligand. When 4 was treated with hydrogen, the phenyl ligand was eliminated as benzene and the dirhenium complexes Re 2 (CO) 8 (μ-SbPh 2 )(μ-H) ( 10 ), and Re 2 (CO) 7 (SbPh 3 )(μ-SbPh 2 )(μ-H) ( 11 ), were formed that contain a bridging hydrido ligand. The doubly SbPh 2 -bridged dirhenium complex Re 2 (CO) 7 (SbPh 3 )(μ-SbPh 2 ) 2 ( 9 ) that has no metal–metal bond was also formed in these two reactions.

V.V. Sharutin1, vvsharutin@rambler.ru O.K. Sharutina1, sharutinao@mail.ru V.S. Senchurin1, senvl@rambler.ru A.N. Neudachina1, neudachina.a@yandex.ru P.V. Andreev2, andreev@phys.unn.ru 1 South Ural State University, Chelyabinsk, Russian Federation 2 Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, Russian Federation Шарутин Владимир Викторович – доктор химических наук, профессор, старший научный сотрудник УНИД, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: vvsharutin@rambler.ru. Шарутина Ольга Константиновна – доктор химических наук, профессор, кафедра аналитической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: sharutinao@mail.ru. Сенчурин Владислав Станиславович – кандидат химических наук, доцент, кафедра органической химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: senvl@rambler.ru Неудачина Анастасия Николаевна – студент, кафедра органической химии, Южно- Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: neudachina.a@yandex.ru Андреев Павел Валерьевич - аспирант, младший научный сотрудник НИЛ кафедры кристаллографии и экспериментальной физики. Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Н. Новгород, пр. Гагарина, 23А. E-mail: andreev@phys.unn.ru Interaction of silver iodide with triphenylstibine in dimethyl sulfoxide has led to the neutral complex iodotris(triphenylstibine)silver (1), whose structure has been established by Xray diffraction analysis. The silver atom has distorted tetrahedral coordination. The angles SbAgSb and SbAgI equal 106.501(13)°, 109.644(13)°, 111.099(13)° и 103.063(13)°, 111.594(14)°, 114.337(14)°, the bond lengths Ag–Sb and Ag–I equal 2.7291(4), 2.7326(4), 2.8087(4) и 2.7600(4) Å. Взаимодействием иодида серебра с трифенилстибином в диметилсульфоксиде синтезирован нейтральный комплекс иодотрис(трифенилстибин)серебро (1), строение которого установлено методом РСА. Атом Ag имеет искаженную тетрагональную координацию. Углы SbAgSb и SbAgI составляют 106,501(13)°, 109,644(13)°, 111,099(13)° и 103,063(13)°, 111,594(14)°, 114,337(14)°, длины связей Ag-Sb и Ag-I равны 2,7291(4); 2,7326(4); 2,8087(4) и 2,7600(4) Å.

Protonation of the highly reactive 1:1 intermediates, produced in the reaction between triphenylstibine and dialkyl acetylenedicarboxylates, by imides (phthalimide and succinimide) leads to vinyltriphenylstibinium salts, which undergo a Michael addition reaction with a conjugate base to produce dialkyl 2-(imido-N-yl)-3-(triphenylstibanylidene)succinates. Silica gel was found to catalyze the stereoselective conversion of dialkyl 2-(imido-N-yl)-3-(triphenylstibanylidene)succinates to electron-poor (Z)-N-vinylimides in solvent-free conditions at 97°C in high conversions.

The catalytic activities of the complexes of Pd, Ru, Co and Rh with PPh3, AsPh3 and SbPh3 ligands have been investigated for the hydroformylation of ethylene in as benzene solvent. All the studied metal complexes, other than that of Rh, with AsPh3 ligand were found to show better hydroformylation catalytic activity than those of their corresponding complexes with PPh3 and SbPh3 ligands.

The reactions of [NBu4]2[ReX5(NO)] (X = Cl, Br) with triphenylstibine have been examined and three new rhenium complexes – [ReCl2(NO)(SbPh3)3] (1), [ReBr2(NO)(SbPh3)3] (2) and [ReBr2Cl(SbPh3)3] (3) – have been obtained. The last one has been isolated in a low yield during slow recrystallization of the complex 2 from a mixture of chloroform and ethanol. The stibine rhenium nitrosyls have been characterized by IR and UV–vis spectroscopy. The X-ray structures of 1 and 3 have been determined. The geometric parameters of 1 have been examined using the density functional theory (DFT) method.

The reaction of Wakamatsu was applied for the preparation of α-acetyl-aminoacids from several unsaturated substrates in very mild conditions in the presence of a cobalt–stibine-modified system in comparison to some classical cobalt–phosphine precursors. The stibine and phosphine ligands used were: triphenylstibine (TPS), o - and p -tritolylstibine ( o -TTS, p -TTS), phenyl(phenylethynyl)mesitylstibine (PPEMS), phenylthienylmesitylstibine (PTMS), p -fluorophenylstibine ( p -TFPS), triphenylphosphine (TPP), o - and - p -tritolylphosphine ( o -TTP, p -TTP).

Tetraphenylantimony nicotinate was prepared in 91% yield by reaction of pentaphenylantimony with triphenylantimony bis(nicotinate) in toluene. Triphenylantimony bis(nicotinate), in turn, was prepared in 87% yield by oxidative addition of pyridine-3-carboxylic acid to triphenylstibine in ether in the presence of hydrogen peroxide. The structure of tetraphenylantimony nicotinate was determined by single-crystal X-ray diffraction. The Sb atom has a distorted trigonal bipyramidal coordination surrounding with the carboxy group in the axial position. The Sb-C distances are 2.118(1), 2.121(1), 2.130(1), and 2.170(1) A, and the Sb-O distance is 2.268(1) A. There is an intramolecular contact between the Sb atom and the carbonyl O atom [3.363(1) A].

Metal ion-catalysed replacement of bromine in 1-amino-2-methyl-4-bromoanthraquinone by triphenylphosphine and triphenylstibine occurs readily under mild conditions to give the respective phosphonio- and stibonio-anthraquinone salts, the carbonyl group acting as a coordination template for the metal ion, facilitating replacement of the halogen. The extent to which the Group 15 element may be involved in hypercoordination from the adjacent carbonyl oxygen atom in the 'onium salts has been investigated by X-ray crystallography. Both salts involve considerable distortion of bond angles about the Group 15 atom in the direction of trigonal bipyramidal geometry, with phosphorus-oxygen (2.661 Angstrom) and antimony-oxygen (2.497 Angstrom) distances which are well within the sum of the van der Waals radii. In both structures, the Group 15 element and the adjacent carbonyl oxygen atom are bent out of the plane of the anthraquinone system. However, the extent of out of plane deformation is smaller in the case of the larger antimony atom, suggesting that there is a genuine hypercoordinative interaction which increases as the Group is descended.

The [ReBrCl2(SbPh3)3] complex has been obtained in the reaction of [But4N]2[ReBr3Cl2(NO)] with an excess of triphenylstibine. The halide ions and stibine molecules of [ReBrCl2(SbPh3)3] are arranged in a meridional fashion. The substitution reactions of the nitrosyl ligand are very rare so the formation of the [ReBrCl2(SbPh3)3] compound in this reaction is particularly interesting.

A series of iridium-based complexes formed in situ, containing pyridine, phosphines, triphenylarsine, triphenylstibine, and triphenylamine as ligands, has been screened for ability to mediate ortho-exchange of hydrogen in a series of model substrates. Improved incorporation into a number of substrate classes has been achieved. The electronic properties and number of ligands at the metal centre are instrumental in determining which catalysts are best suited to exchange in any given substrate.

μ-Oxo-bis[(4-methylbenzenesulfonato)triphenylantimony] (I) and μ-oxo-bis[(2,5-dimethylbenzenesulfonato)triphenylantimony] (II) were synthesized by reacting triphenylstibine Ph3Sb with tri-p-tolylbismuth bis(4-methylbenzenesulfonate) and tri-p-tolylbismuth bis(2,5-dimethylbenzenesulfonate), respectively, in toluene in the presence of air moisture. According yo X-ray diffraction data, the antimony atoms in the compounds synthesized have a distorted trigonal bipyramidal configuration. The SbOSb angles are equal to 138.5(2)° and 180°, respectively. A bent molecule I contains the Sb(1)···Sb(2) (3.690(1) A) and Sb···S(1,2) (3.521(2), 3.559(2) A) intramolecular contacts. In a linear molecule II, the Sb···S distances are equal to 3.438(1) A.

Adducts of triorganophosphine, triphenylarsine, and triphenylstibine with silver(I) nitrite have been synthesized and characterized both in solution (1H, 31P NMR) and in the solid state (IR, single-crystal X-ray structure analysis). In addition aggregates of AgNO2 and ER3 (E = P, As, Sb) have been identified in solution by electrospray ionization mass spectrometry (ESI-MS). The topology of the structures in the solid state was found to depend on the nature of ER3 and on the stoichiometric ratio AgNO2:ER3. The adducts AgNO2:EPh3 (1:1) (E = P or Sb) are one-dimensional polymers, the role of NO2- being to bridge successive metal atoms by coordination of the two oxygens to one silver atom and the nitrogen lone pair to a successive Ag. The adduct AgNO2:P(o-tolyl)3 (1:1) is mononuclear, due to steric hindrance of the phosphine, the nitrite being O,O‘-bidentate, a rare example of a quasi-linear P−Ag−X array. AgNO2:P(p-F−C6H4)3 (1:1) is a dimer, the nitrite being coordinated through both oxygens, the first uniden...

The complexes, [Co(CNC 4 H 9 - n ) 4 (SbPh 3 ) 2 ](ClO 4 ) 2 , [Co(CNC 6 H 11 ) 4 (SbPh 3 ) 2 ](ClO 4 ) 2 , [Co(CNC 6 H 11 ) 4 (OSbPh 3 ) 2 ](ClO 4 ) 3 , and [Co(CNCH 2 Ph) 4 (OSbPh 3 ) 2 ](BF 4 ) 3 , have been synthesized by reaction of excess SbPh 3 with the Co(II)–alkylisocyanide salts. With CNC 6 H 11 , the Co(II) complex can be isolated, continued reaction in solution producing the Co(IIl) complex. With CNCH 2 Ph, reaction proceeds more rapidly through a Co(II) complex directly to the Co(III) complex isolated. With CNC 4 H 9 - n , only the Co(II) complex is observed; attempted further reaction causes decomposition to OSbPh 3 . Characterization of the complexes is primarily in the solid state due to limited stability in solution. Coordination stereochemistries for both Co(II) and Co(III) complexes appear to be trans -substituted octahedral. Magnetic moments for [Co(CNC 4 H 9 - n ) 4 (SbPh 3 ) 2 ](ClO 4 ) 2 and [Co(CNC 6 H 11 ) 4 (SbPh 3 ) 2 ](ClO 4 ) 2 are low-spin ( μ eff =1.94 BM, 2.27 BM, respectively), as expected, while [Co(CNCH 2 Ph) 4 (OSbPh 3 ) 2 ](BF 4 ) 3 and [Co(CNC 6 H 11 ) 4 (OSbPh 3 ) 2 ](C1O 4 ) 3 are intermediate-spin ( μ eff =3.30, 3.70 BM, respectively), as expected. Six-coordinate Co(III) complexes, in which both Co(II) and SbPh 3 have been oxidized in the reaction, appear to be favored over the six-coordinate Co(II) complexes. Reactions of SbPh 3 with pentakis (alkylisocyanide)cobalt(II) complexes are thus drastically different from reactions with PPh 3 and even AsPh 3 .

Bis(2,4,6-tribromophenoxy)triphenylantimony was synthesized by reacting triphenylstibine with 2,4,6-tribromophenol in ether in the presence of hydrogen peroxide. Its structure was determined by X-ray diffraction analysis. The coordination polyhedron of the Sb atom is a distorted trigonal bipyramid with the aroxy groups in the axial positions. The bond lengths are Sb(1)–C(Ph) 2.095(4)–2.106(4) A and Sb(1)–O(1,2) 2.099(3) and 2.092(3) A. The value of the O(1)SbO(2) axial angle is 177.3(1)°.

Interesting results, presenting the use of different stibine ligands in amidocarbonylation of cyclohexene and 1-pentene catalyzed by Co2(CO)8, not only enhance the activity of catalyst but also increases the selectivity in comparison to classical phosphinic ligands, have been reported. The stibine and phosphine ligands used were triphenylstibine (TPS), o- and p-tritolylstibine, (o-TTS, p-TTS) 2,4,6-trimesitylstibine (TMS), p-trifluorophenylstibine (p-TFPS), triphenylphosphine (TPP), o- and p-tritolylphosphine (o-TTP, p-TTP), respectively. All the reactions were carried out in a very mild syngas pressure (25 bar).

Tetraphenylantimony arenesulfonates and diphenylbismuth arenesulfonates were prepared by reaction of triphenylbismuth bis(arenesulfonates) with triphenylstibine in toluene at 25°C. The crystal and molecular structure of diphenylbismuth 2,4-dimethylbenzenesulfonate was studied by single crystal X-ray diffraction. The molecules of the compound in the crystal form chains of Ph2BiOSO2C6H3Me2-2,4 fragments linked with oxygen atoms of the sulfo group of the bridging arenesulfonate ligand.

Reaction of triphenylstibine with furfuraloxime in the presence of hydrogen peroxide in water-ether solution forms μ-oxobis[triphenyl(furfuraloximato)antimony(V)] in 90% yield. This complex has a dimeric structure in which two antimony atoms are bound with the bridge oxygen atom and two bridge oxime groups coordinating the metal atom by the oxygen as well as by the nitrogen atoms to form bicyclo[2.2.1]heptane fragment. SbOSb angle is 125.5(3)°, the bonds between the antimony atom and the bridge oxygen atoms [1.957(6) and 1.946(5) A] are shorter than with the oxygen atoms of oxime groups [2.146(6) and 2.148(6) A].

The complex [Pt(9S3)(SbPh3)(Ph)](PF6) forms directly from [Pt(9S3)(SbPh3)2](PF6)2 during the room temperature crystallization of the latter in nitromethane. The crystal structure shows a five-coordinate Pt(II) center containing the tridentate thiacrown ligand, a Sb donor from the triphenylstibine ligand, and a σ-coordinating phenyl group. The phenyl group forms via Sb–C bond cleavage from one of the SbPh3 ligands in the bis complex.

The work reports the unexpected reaction of diphenyldibromo antimonates (III) with PtCl2 and cis-[PtCl2(PPh3)2]. The reaction gives triphenylstibine containing PtII complexes viz. cis-[PtBr2(SbPh3)2] (1), trans-[[PtBr(Ph)(SbPh3)2] (2), [NMe4][PtBr3(SbPh3)] (3), and cis-[PtBr2(PPh3)(SbPh3)] (4). All the complexes were characterised by elemental analyses, IR, Raman, 195Pt NMR, FAB mass spectroscopy and X-ray crystallography. A plausible mechanism via the phenyl migration is proposed for the formation of these complexes. The average Pt–Br distance in 1 is 2.456(2) A, in 2 2.496 A(trans to Ph) while in 3 it is 2.476 A (trans to Sb) implying a comparable trans influence of Ph3Sb and Ph3P. Transeinflus von Triphenylantimon: Die Kristallstrukturen von cis-[PtBr2(SbPh3)2], trans-[PtBr(Ph)(SbPh3)2], [NMe4][PtBr3(SbPh3)] und cis-[PtBr2(SbPh3)(PPh3)] Es wird uber die unerwartete Reaktion von [Ph2SbBr2]– mit PtCl2 und cis-[PtCl2(PPh3)2] berichtet, die die Platin(II)-Komplexe cis-[PtBr2(SbPh3)2] (1), trans-[[PtBr(Ph)(SbPh3)2] (2), [NMe4][PtBr3(SbPh3)] (3) und cis-[PtBr2(PPh3)(SbPh3)] (4) ergibt. Die Komplexe werden durch Elementaranalyse, IR, Raman, 195Pt-NMR, FAB-Massenspektrometrie und Rontgenstrukturanalyse charakterisiert. Fur die Bildung der Komplexe wird ein Reaktionsmechanismus durch Ligandenaustausch vorgeschlagen. Der mittlere Pt–Br-Abstand betragt in 1: 2,456 A, in 2: 2,496 A (trans zu Ph), in 3: 2,476 A (trans zu Sb), was auf einen ahnlichen Transeinflus von Ph3Sb und Ph3P hinweist.

The triphenylstibine and bismuthine complexes [Cu(EPh3)(LH)2X] (LH = N, N-dimethyl-N′-phenylthiourea) (dmptH), N, N-dibutyl-N′-phenylthiourea (dbptH) or 1, 3-thiazolidine-2-thione (tzdtH); E = Sb or Bi; X = Cl, Br or I have been prepared and characterized on the basis of analytical, IR. electronic (UV-Vis), 1H and I3C NMR, FAB mass and conductivity measurements. In all cases there is a distorted tetrahedral environment around Cu(I) and the ligand (LH) binds through the thionc sulphur atom to copper(1). This is confirmed by FTIR spectra of the complexes. The complexes show v(Cu-Sb) in the range 180–195 cm−1.

The reaction of trans -[RuCl 2 (SbPh 3 ) 4 ] ( 1) with 1,9-dimethylpurine-6-thione, Me 2 tp, in CHCl 3 , produced trans -[RuCl 2 (Me 2 tp)(SbPh 3 ) 2 ] ( 2) . Single crystals containing molecules of 2 could be obtained from chlorobenzene. The X-ray diffraction analysis showed that only one Me 2 tp molecule enters the coordination sphere by removing two SbPh 3 molecules even in the presence of excess chelating agent (up to 3:1). Me 2 tp chelates through S and N(7) and occupies the two equatorial positions trans to the Sb atoms; the Cl − donors are at the apical sites. The Ru–S and Ru–N bond distances are 2.411(3) and 2.157(10) A, respectively, whereas the S/N(7) bite distance is 3.06(1) A. The Me 2 tp ligand is sandwiched between the two crystallographically independent C 6 H 5 Cl molecules with which it has stacking interactions. An attractive intramolecular interaction takes place between the (C(8))H purine proton and the π-system of a Ph group from SbPh 3 , the distance between H(8) and the centroid of Ph being 2.79(1) A. The reaction of 1 with other N-donor ligands (L) such as 3,5-dimethylpyridine (Lut) and 1,4-pyrazine (Pyz) up to a L:Ru molar ratio of 100 caused the removal of only two SbPh 3 molecules out of four and it was not able to remove the Cl − ligands. It was carried out with refluxing CHCl 3 , under anaerobic conditions, and brought about the formation of trans,cis,cis -[RuCl 2 (Lut) 2 (SbPh 3 ) 2 ] ( 3) and trans,cis,cis -[RuCl 2 (Pyz) 2 (SbPh 3 ) 2 ] ( 4) . The 1 H NMR data for 2 are in agreement with a H(8)⋯π(Ph) interaction; a large shielding effect on H(8) taking place. The signals of the H(2) and H(6) protons of Lut and Pyz in 3 and 4 undergo large down-field effects, when compared with data for the free ligands, in agreement with a significant trans influence by Sb.

Silver(I) cyanoximate complexes Ag{ONC(CN)-R} (R = COPh, {L1}; COC(CH3)3, {L2}; benzothiazol-2-yl, {L3}) with triphenylphosphine and -stibine of compositions Ag(PPh3)n{L} (n = 2, 4) and Ag(SbPh3)n{L} (n = 3 for {L1} and {L2}, n = 2 for {L3}) were synthesized by the reaction of the components in acetonitrile solution and characterized by elemental analyses and IR spectroscopy. The crystal structures of Ag(SbPh3)3{L} (L = {L1} (1), {L2} (2), Ag(SbPh3)2{L3} ∙ CH3CN (3) and Ag(PPh3)2{L1} ∙ CH3CN (4), have been determined by X-ray diffraction. For all the compounds examined the coordination environment of the silver atom has the geometry of a distorted terahedron ([AgP2NO] (4); [AgSb3N] (1), (2); [AgSb2N2] (3)). The bis adducts Ag(EPh3)n{L} adopt molecular structures, in which the organic anions are coordinated in bidentate chelate fashion via the nitroso nitrogen atom and the oxygen (nitrogen for {L3}) atom of the substituent R. In the tris-stibino complexes (Ag-Sb 2.670(4) - 2.7748(8) Å; Sb-Ag-Sb 108.87(4) - 115.00(2)°) the cyanoximates are unidentate ligands and coordinated via the nitroso nitrogen atoms (Ag-N ca. 2.35(1) Å). The different behaviour of N ,O and N,N chelating cyanoximes under the same conditions suggests, that the Sb donor triphenylstibine is able to substitute the oxygen atoms in the silver(I) coordination sphere, but not the nitrogen ones. This causes the formation of 1:3 adducts of Ag{L} with SbPh3 for N ,O donors {L1} and {L2}, and only 1:2 for N,N donor anionic {L3}.

The syntheses of [Mn 2 (CO) 10− x (SbPh 3 ) x ] ( x =1 or 2), [Re 2 (CO) 9 (SbPh 3 )], [Mn(CO) 5 (SbPh 3 )][CF 3 SO 3 ], [M(CO) 4 Cl(SbPh 3 )], fac -[M(CO) 3 Cl(SbPh 3 ) 2 ] (M=Mn or Re) and mer,trans -[Mn(CO) 3 Cl(SbPh 3 ) 2 ] are reported. The complexes have been characterised by chemical analysis, IR and multinuclear NMR ( 1 H, 13 C{ 1 H} and 55 Mn) spectroscopies, and FAB mass spectrometry. The crystal structure of [Mn 2 (CO) 9 (SbPh 3 )] established the axial position of the SbPh 3 ligand (Mn–Sb 2.525(1), Mn–Mn 2.909(1) A) and that of [Mn(CO) 5 (SbPh 3 )][CF 3 SO 3 ] confirmed the cation structure (Mn–Sb 2.596(3) A). The crystal structure of fac -[Re(CO) 3 Cl(SbPh 3 ) 2 ] establishes the stereochemistry (Re–Sb 2.726(1), 2.729(2) A). Differences in the products/isomers produced in reactions of [M 2 (CO) 10 ] and [M(CO) 5 Cl] with SbPh 3 and with the corresponding PR 3 and AsR 3 ligands are identified and discussed.

Crystals of cis-[PtCl2(SbPh3)2] (1) are monoclinic, space group P2 1 /a with a=20.5708(12), b=10.1942(4), c=33.3984(15) A , β=94.394(4)° and Z=8 . Substitution of chloride for iodide yields trans-[PtI2(SbPh3)2] (2), the crystals of which are monoclinic, space group P2 1 /c with a=18.108(4), b=10.102(2), c=19.115(5) A , β=95.241(16°) and Z=4 . The average PtCl distance in 1 is 2.338(12) A, implying a trans influence of triphenyl stibine comparable with that of triphenyl phosphine, as opposed to what has been reported earlier. IR and Raman data for 1 and 2 are reported and discussed.

Rare earth metal ions containing polymer ternary complexes were synthesized and characterized. The functional polymers investigated were polymer-bond triphenylphosphine (PBDP), polymer-bond triphenylarsine (PBDAs), polymer-bond triphenylstibine (PBDSb), and polymer-bond triphenylbismuthine (PBDBi) as polymer ligands. Several substances, such as thenoyltrifluoroacetone (TTA), and 8-hydroxyquinoline (oxin), phenanthroline (phen) were used as low molecular weight ligands. The results show that TTA is the best low molecular weight ligand among them. The fluorescence properties of synthesized complexes were investigated; PBDAs is a better polymer ternary complex that possesses stronger fluorescence intensity coordinated with any low molecular weight ligand. The fluorescence lifetimes of Eu3+-containing polymer ternary complexes are between 0.350 and 0.469 MS. The reaction conditions of the formation and stability of rare earth metal ions–polymer–TTA ternary complexes are discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1605–1611, 1998