Ferrocene-Mn π-interaction in the complex [Fc2Bpz2Mn(THF)Cl]

The ferrocene-based bis(pyrazol-1-yl)borate ligands [Fc₂Bpz₂]⁻ ([2]⁻) and [Fc₂Bpz^Ph₂]⁻ ([2^Ph]⁻) have been prepared (Fc: ferrocenyl; pz: pyrazol-1-yl; pz^Ph: 3-phenylpyrazol-1-yl). Treatment of [2]⁻ and [2^Ph]⁻ with MnCl₂ in THF leads to the complexes [Fc₂Bpz₂Mn(THF)(μ-Cl)₂Mn(THF)pz₂BFc₂] (3) and [Fc₂Bpz^Ph₂Mn(THF)Cl] (3^Ph), respectively, which have been structurally characterized by X-ray crystallography. While there is clearly no ferrocene-Mn^II π-coordination in the solid-state structure of 3, short Mn^II-C₅H₄ contacts are established in 3^Ph (shortest Mn-C distances: 2.780(2) Å, 2.872(2) Å). The cyclic voltammograms of K[2^Ph] and 3^Ph show the first ferrocene/ferricinium redox wave of 3^Ph to be shifted anodically by 0.60 V compared with the first Fe^II/Fe^III transition of K[2^Ph].     

Synthesis of bismuth complexes from bismuth iodide and ammonium and phosphonium salts

The complexes [Et₂NH₂] ₃ ⁺ [BiCl₆]^3? (I), [NH₄]⁺[BiI₄(C₅H₅N)₂]^?·2C₅H₅N (II), [Ph₃MeP] ₂ ⁺ [BiI₅]^2? (III), [Ph₃MeP] ₂ ⁺ [BiI₅(C₅H₅N)]^2?·C₅H₅N (IV), [Ph₃MeP] ₃ ⁺ [Bi₃I₁₂]^3? (V), [Ph₃(i-Pr)P] ₃ ⁺ [Bi₃I₁₂]^3?·2Me₂C=O (VI), [Ph₃BuP] ₂ ⁺ [Bi₂I₈·₂Me₂C=O]^2? (VII), and [Ph₃BuP] ₂ ⁺ [Bi₂I₈·2Me₂S=O]^2? (VIII) were obtained by reactions of bismuth iodide with ammonium and phosphonium iodides in acetone, pyridine, or dimethyl sulfoxide.     

Mercapto derivatives of triorganotin Y,C,Y-pincer complexes: Role of Y,C,Y-chelating ligands in a new coordination mode of organotin compounds

We report the use of triorganotin fragments R₂L^1-2Sn containing N,C,N and O,C,O-ligands L^1-2(L¹ = C₆H₃(Me₂NCH₂)₂-2,6⁻, L² = C₆H₃(^tBuOCH₂)₂-2,6⁻) on stabilization of both thiol-form in R₂L^1-2Sn-2-SPy (2-SPy = pyridine-2-thiolate) and thione-form in R₂L^1-2Sn(mimt) (mimt = 1-methylimidazole-2-thiolate) of the polar groups. Treatment of ionic organotin compounds [Me₂L¹Sn]⁺[Cl]⁻ (1) and [Ph₂L²Sn]⁺[OTf]⁻ (2) with appropriate sodium salts Na-2-SPy and Na(mimt) resulted in the isolation of Me₂L¹Sn-2-SPy (3), Ph₂L²Sn-2-SPy (4), Me₂L¹Sn(mimt) (5), Ph₂L²Sn(mimt) (6). While polar group 2-SPy exists in its thiol-tautomeric form in compounds 3 and 4, the second polar group (mimt) has been stabilized as the thione-tautomeric form by triorganotin fragments R₂L^1-2Sn in compounds 5 and 6. The products were characterized by ¹H, ¹³C and ¹¹⁹Sn NMR and IR spectroscopy, ESI/MS, elemental analyses and structures of 3, 6 were determined by X-ray diffraction study. The reactivity of compound 4 containing non-coordinated nitrogen atom of 2-SPy polar group towards CuCl and AgNO₃ is also reported. The reactions led to isolation of organotin compounds Ph₂L²SnCl (7) and Ph₂L²SnNO₃ (8) as the result of polar group transfer. The mechanism of this reaction has been investigated and compounds Ph₃Sn-2-SPy (9) and Ph₂L²Sn-4-SPy (10) (4-SPy = pyridine-4-thiolate) have been prepared for this purpose.     

Palladium complexes of multidentate pyrazolylmethyl pyridine ligands: Synthesis,structures and phenylacetylene polymerization

The compounds, 2,6-bis(3,5-dimethylpyrazol-1-ylmethyl)pyridine (_MeNˆNˆN) (L1) and 2,6-bis(3,5-ditertbutylpyrazol-1-ylmethyl)pyridine (_tBuNˆNˆN) (L2), react with either [Pd(NCMe)₂Cl₂] or [Pd(COD)ClMe] to form the mononuclear palladium complexes [Pd(_MeNˆNˆN)Cl₂] (1), [Pd(_MeNˆNˆN)ClMe] (2), [Pd(_tBuNˆNˆN)Cl₂] (3) and [Pd(_tBuNˆNˆN)ClMe] (4). Reactions of 1, 2 and 4 with the halide abstractor, NaBAr₄ (Ar = 3,5-(CF₃)₂C₆H₃), led to the formation of stable tridentate cationic species [Pd(_MeNˆNˆN)Cl]⁺(5), [Pd(_MeNˆNˆN)Me]⁺ (6) and [Pd(_tBuNˆNˆN)Cl]⁺ (7) respectively. The analogous carbonyl linker cationic species [Pd{(3,5-Me₂pz-CO)₂-py}Cl]⁺ (9) and [Pd{(3,5-^tBu₂pz-CO)₂-py}Cl]⁺ (10), prepared by halide abstraction of the neutral complexes [Pd{(3,5-Me₂pz-CO)₂-py}Cl₂] and [Pd{(3,5-^tBu₂pz-CO)₂-py}Cl₂] by NaBAr₄, were however less stable with t_1/2 of 14 and 2 days respectively. Attempts to crystallize 1 and 3 from the mother liquor resulted in the isolation of the salts [Pd(_MeNˆNˆN)Cl]₂[Pd₂Cl₆] (11) and [Pd(_tBuNˆNˆN)Cl]₂[Pd₂Cl₆] (12). Although when complexes 1–4 were reacted with modified methylaluminoxane (MMAO) or NaBAr₄, no active catalysts for ethylene oligomerization or polymerization were formed, activation with silver triflate (AgOTf) produced active catalysts that oligomerized and polymerized phenylacetylene to a mixture of cis-transoidal and trans-cisoidal polyphenylacetylene.     

Reduction of 1-chloro-1,2,3,4,5-pentaphenylsilole: formation of silole monoanion and dianion

The reduction of 1-chloro-1,2,3,4,5-pentaphenylsilole, (C₄Ph₄SiPhCl, 1) with 2 equiv lithium gave the pentaphenylsilole anion [C₄Ph₄SiPh]⁻ (2), silole dianion [C₄Ph₄Si]²⁻ (3), and hexaphenylsilole C₄Ph₄SiPh₂ (4). 2, 3, and 4 from the reaction mixture were characterized by ²⁹Si NMR spectroscopy. The ²⁹Si chemical shift of 3.7 ppm for 2 is shifted upfield as compared to that of previously reported t -butyltetraphenylsilole anion Li[C₄Ph₄SitBu], but shifted downfield compared to that of the other silole monoanion such as Li[C₄Me₄SiSiMe₃], indicating the delocalization of silole anion through the 5-membered ring. Derivatization of the reaction mixture with iodomathane gave C₄Ph₄SiPh₂ (4), C₄Ph₄SiMePh (5), and C₄Ph₄SiMe₂ (6), which were characterized by ¹H, ¹³C, and ²⁹Si NMR spectroscopy. The silole dianion 3 could be either from the continuous reduction of 1 with lithium or from the disproportionation of 2. The reduction of 1 with excess lithium in THF gave the silole dianion [C₄Ph₄Si]²⁻ in about 70% yield.     

Structural characterization of [Fe(NO)(mnt)2] salts

The iron dithiolene compounds [Fe₂(mnt)₄]²⁻ [1]²⁻ and [Fe(NO)(mnt)₂]ⁿ (n = 1−, [2]¹⁻; n = 2−, [2]²⁻) ([mnt]²⁻ = maleonitriledithiolate = [(NC)₂C₂S₂]²⁻) have been characterized structurally by X-ray diffraction as their [Et₄N]⁺ salts at 100 K. Dianion [2]²⁻ is prepared from [2]¹⁻ by reduction with Na[Et₃BH] and is observed to have a bent Fe-NO angle at 149.9(5)° in contrast to the linear configuration of Fe-NO in [2]¹⁻ (180.0°). The change from linear to bent binding mode for NO, an increase of more than 0.1 Å in the Fe-N bond length, and the relative invariance of the Fe-S distances for [2]²⁻ versus [2]¹⁻ indicate that the NO ligand is the site of reduction. The [Et₃NH]⁺ complex of [2]¹⁻ was also identified by crystallography and found to have hydrogen bonding contacts between [Et₃NH]⁺ and the cyano nitrogen atom of an [mnt]²⁻ ligand. Furthermore, relatively close S?S contacts (3.602-3.615 Å) occur between [2]¹⁻ anions, which pack together in an offset, head-to-head fashion. These S?S contacts are absent in the structure of [Et₄N][2]. Infrared spectra show an energy decrease for, and a significant broadening of, the NO bond stretching absorption peak in [2]²⁻, which is consistent with a bent NO ligand sampling a range of conformations both by facile pivoting about the Fe-N axis and by a breathing of the Fe-NO angle.     

Selenium-capped trimolybdenum and tritungsten carbonyl clusters [Se2M3(CO)10] (M = Mo, W)

A facile synthesis of the novel selenium-capped trimolybdenum and tritungsten ring carbonyl clusters [Se₂M₃(CO)₁₀]²⁻ (M = Mo, 1; W, 4) have been achieved. The selenium-capped trimolybdenum cluster compound [Et₄N]₂[Se₂Mo₃(CO)₁₀] ([Et₄N]₂[1]) can be obtained from the reaction of the trichromium cluster compound [Et₄N]₂[Se₂Cr₃(CO)₁₀] with 4 equiv. of Mo(CO)₆ in refluxing acetone. On the other hand, when [Et₄N]₂[Se₂Cr₃(CO)₁₀] reacted with 4 equiv. of W(CO)₆ in refluxing acetone, the planar cluster compound [Et₄N]₂[Se₂W₄(CO)₁₈] ([Et₄N]₂[3]) was isolated, which could further transform to the tritungsten cluster compound [Et₄N]₂[Se₂W₃(CO)₁₀] ([Et₄N]₂[4]) in good yield. Alternatively, clusters 1 and 4 could be formed from the reactions of the monosubstituted products [Et₄N]₂[Se₂Cr₂M(CO)₁₀] (M = Mo; W, [Et₄N]₂[2]) with 3 equiv. of M(CO)₆ in acetone, respectively. Complexes 1-4 are fully characterized by IR, ⁷⁷Se NMR spectroscopy, and single-crystal X-ray analysis. Clusters 1, 2, and 4 are isostructural and each display a trigonal bipyramidal structure with a homometallic M₃ ring (M = Mo, 1; W, 4) or a heterometallic Cr₂W ring that is further capped above and below by μ₃-Se atoms. Further, the intermediate planar complex 3 exhibits a Se₂W₂ square with each Se atom externally coordinated to one W(CO)₅ group. This paper describes a systematic route to a series of selenium-capped trimetallic carbonyl clusters and the formation and the structural features of the resultant clusters are discussed.     

Alternative syntheses and X-ray diffraction analyses of the parent tricarbaborane compounds [nido-7,8,9-C3B8H11], [nido-7,8,10-C3B8H11] and [1-(η-C5H5)-closo-1,2,4,10-FeC3B8H11]

Reaction of the neutral tricarbaborane nido-7,8,9-C₃B₈H₁₂ (1) with triethylamine in CH₂Cl₂ led to quantitative deprotonation and isolation of the corresponding Et₃NH⁺ salt of the [nido-7,8,9-C₃B₈H₁₁]⁻ anion (2). This was converted into PSH⁺ and Me₄N⁺ salts via metathetic cation exchange. Heating of the solid Me₄N⁺[7,8,9-C₃B₈H₁₁]⁻ in mineral oil at 350 °C for 2 h resulted in thermal rearrangement and isolation of the cage isomeric compound Me₄N⁺[7,8,10-C₃B₈H₁₁]⁻. Finally, compound 1 was directly complexed via reaction with [CpFe(CO)₂]₂ (Cp = η⁵-C₅H₅) to generate the ferratricarbollide sandwich [1-Cp-closo-1,2,4,10-FeC₃B₈H₁₁] (4) in 60% yield. The structures of all the generic compounds of tricarbollide chemistry, 1 (PSH⁺ salt), 2 (MePPh₃⁺salt), and 4, were established unambiguously by an X-ray diffraction analysis.     

Antimony(V) catecholato complexes based on 4,5-dialkylsubstituted o-benzoquinone. The spectroscopic and electrochemical studies. Crystal structure of [Ph4Sb][Ph2Sb(4,5-Cat)2]

Triphenylantimony(III) and triethylantimony(III) readily react with 4,5-(1,1,4,4-tetramethyl-butane-1,4-diyl)-o-benzoquinone to form catecholato complexes R₃Sb(4,5-Cat) (R = Ph (1), Et (2); 4,5-Cat is dianionic 4,5-(1,1,4,4-tetramethyl-butane-1,4-diyl)-catecholate). In polar solvents (CHCl₃, acetone) complex 1 transforms easily to ionic complex compound [Ph₄Sb]⁺[Ph₂Sb(4,5-Cat)₂]⁻ (3) with diphenyl-bis-[4,5-(1,1,4,4-tetramethyl-butane-1,4-diyl)-catecholato]antimony(V) complex anion. Complexes were characterized by IR, ¹H, ¹³C NMR spectroscopy, cyclic voltammometry. Molecular structure of 3·CHCl₃ was confirmed by X-ray analysis. Cyclic voltammometry of 1 and 3 shows that both complexes undergo reversible one-electron oxidation to quite stable paramagnetic o-semiquinonato species [Ph₃Sb(4,5-SQ)]⁺ and [Ph₂Sb(4,5-SQ)(4,5-Cat)] (0.75 and 0.49 V in CH₂Cl₂ vs. Ag/AgCl/KCl, respectively).     

A homoleptic SPS-based complex and a double-cubane-type sulfur cluster of an actinide element

Treatment of UI₃(THF)₄ with [M(Et₂O)][SPS^Me] (M = Li, K; [SPS^Me]⁻ = 1-methyl-2,6-bis(diphenylphosphine sulfide)-3,5-diphenylphosphinine anion) gave the cationic tris SPS complex [U(SPS^Me)₃]I (1). Similar reaction of U(BH₄)₃(THF)₃ and [M(Et₂O)][SPS^Me] afforded, in addition to the [U(SPS)₃]⁺ cation, crystals of the sulfido complex [U{(μ₃-S)₄U₃(SPS^Me)₃(BH₄)₃}₂] (2). The metal environment in 1 is a tricapped trigonal prism and the core of the heptanuclear cluster 2 is a corner-shared double-cubane.     

Synthesis and ethylene polymerization behavior of {MeB(3-Ph-pyrazolyl)3}TiCl3

The new methyl-tris(pyrazolyl)borate reagents Li[MeTp^Ph] (1) [MeTp^Ph]⁻ = MeB(3-Ph-pyrazolyl)₃⁻) and Tl[MeTp^Ph] (2) react with TiCl₄ to afford (MeTp^Ph)TiCl₃ (3) in 77% and 81% yield respectively. 2 reacts with ZrCl₄ and HfCl₄ to yield mixtures of products. The reaction of 1 with TiCl₃(THF)₃ proceeds with B-N bond cleavage to afford TiCl₃(3-Ph-pyrazole)(THF)₂ as the major product (30%). The reaction of 3 with MeLi (3 equiv) yields 1 (60%) and reduced Ti species, via apparent displacement of [MeTp^Ph]⁻ and generation of unstable TiCl₄Me_4−x species. Under MAO activation conditions (MAO = methylalumoxane), 3 polymerizes ethylene to linear polyethylene. 3/MAO is significantly more active in ethylene polymerization than the hydrido-tris(pyrazolyl)borate analogue {HB(3-Ph-pyrazolyl)₃}TiCl₃/MAO.     

Syntheses, crystal structures and DFT studies of [Me3EM(CO)5] (E = Sb, Bi; M = Cr, W), cis-[(Me3Sb)2Mo(CO)4], and [Bu3BiFe(CO)4]

Syntheses of [Me₃SbM(CO)₅] [M = Cr (1), W (2)], [Me₃BiM(CO)₅] [M = Cr (3), W (4)], cis-[(Me₃Sb)₂Mo(CO)₄] (5), [^tBu₃BiFe(CO)₄] (6), crystal structures of 1-6 and DFT studies of 1-4 are reported.     

Iridium(III) and rhodium(III) cyclometalated complexes containing sulfur and selenium donor ligands

Treatment of [M(Buppy)₂Cl]₂ (M=Ir (1), Rh (2); BuppyH=2-(4^′-tert-butylphenyl)pyridine) with Na(Et₂NCS₂), K[S₂P(OMe)₂], and K[N(Ph₂PS)₂]₂ afforded monomeric [Ir(Buppy)₂(S^∧S)] (S^∧S=Et₂NCS₂ (3), S₂P(OMe)₂ (4), N(PPh₂S)₂ (5)) and [Rh(Buppy)₂(S^∧S)] (S^∧S=Et₂NCS₂ (6), S₂P(OMe)₂ (7), N(PPh₂S)₂ (8)), respectively. Reaction of 1 with Na[N(PPh₂Se)₂] gave [Ir(Buppy)₂{N(PPh₂Se)₂}] (9). The crystal structures of 3, 4, 7, and 8 have been determined. Treatment of 1 or 2 with AgOTf (OTf=triflate) followed by reaction with KSCN gave dinuclear [{M(Buppy)₂}₂(μ-SCN)₂] (M=Ir (10), Rh (11)), in which the SCN⁻ ligands bind to the two metal centers in a μ-S,N fashion. Interaction of 1 and 2 with [Et₄N]₂[WQ₄] gave trinuclear heterometallic complexes [{Ir(Buppy)₂}₂(μ-WQ₄)] (Q=S (12), Se (13)) and [{Rh(Buppy)₂}₂{(μ-WQ)₄}] (Q=S (14), Se (15)), respectively. Hydrolysis of 12 led to formation of [{Ir(Buppy)₂}₂{W(O)(μ-S)₂(μ₃-S)}] (16) that has been characterized by X-ray diffraction.     

Mono and dinuclear rhodium, iridium and ruthenium complexes containing chelating 2,2′-bipyrimidine ligands: Synthesis, molecular structure, electrochemistry and catalytic properties

The mononuclear cations [(η⁵-C₅Me₅)RhCl(bpym)]⁺ (1), [(η⁵-C₅Me₅)IrCl(bpym)]⁺ (2), [(η⁶-p-PrⁱC₆H₄Me)RuCl(bpym)]⁺ (3) and [(η⁶-C₆Me₆)RuCl(bpym)]⁺ (4) as well as the dinuclear dications [{(η⁵-C₅Me₅)RhCl}₂(bpym)]²⁺ (5), [{(η⁵-C₅Me₅)IrCl}₂(bpym)]²⁺ (6), [{(η⁶-p-PrⁱC₆H₄Me)RuCl}₂(bpym)]²⁺ (7) and [{(η⁶-C₆Me₆)RuCl}₂(bpym)]²⁺ (8) have been synthesised from 2,2′-bipyrimidine (bpym) and the corresponding chloro complexes [(η⁵-C₅Me₅)RhCl₂]₂, [(η⁵-C₅Me₅)IrCl₂]₂, [(η⁶-PrⁱC₆H₄Me)RuCl₂]₂ and [(η⁶-C₆Me₆)RuCl₂]₂, respectively. The X-ray crystal structure analyses of [3][PF₆], [5][PF₆]₂, [6][CF₃SO₃]₂ and [7][PF₆]₂ reveal a typical piano-stool geometry around the metal centres; in the dinuclear complexes the chloro ligands attached to the two metal centres are found to be, with respect to each other, cis oriented for 5 and 6 but trans for 7. The electrochemical behaviour of 1-8 has been studied by voltammetric methods. In addition, the catalytic potential of 1-8 for transfer hydrogenation reactions in aqueous solution has been evaluated: All complexes catalyse the reaction of acetophenone with formic acid to give phenylethanol and carbon dioxide. For both the mononuclear and dinuclear series the best results were obtained (50 °C, pH 4) with rhodium complexes, giving turnover frequencies of 10.5 h⁻¹ for 1 and 19 h⁻¹ for 5.     

Synthesis and structure of fluorosilicic acid compounds with 4-aminobenzoic acid and with 4-aminobenzenesulfonamide: The role of H-bonding in crystal structure formation

Preparation and characterization of the ammonium hexafluorosilicate salts, 2[R]⁺[SiF₆]²⁻ (R = 4-(aminosulfonyl)benzenammonium) (1), and 2[R]⁺[SiF₆]²⁻.4H₂O (R = 4-carboxybenzenammonium), (2), are described. These salts, prepared from the reaction of the 4-aminobenzenesulfonamide or the 4-aminobenzoic acid with fluorosilicic acid, were characterized by IR, mass spectrometry and X-ray diffraction. 1 and 2 crystallize in monoclinic crystal system (space group P2₁/c and P2₁/n, respectively), with Z = 2 in both cases. Compounds exhibit an extensive system of hydrogen bonding.     

[Me8Pt4ReS4] and related PtMe2-containing clusters derived from tetrathiorhenate

The reactions of Pt₂Me₄(μ-SMe₂)₂ and [ReS₄]⁻ in MeCN solution have been investigated. The resulting polyalkylated clusters: Et₄N[ReS₄PtMe₂] (Et₄N[1]), Et₄N[ReS₄(PtMe₂)₂] (Et₄N[2]), and Et₄N[ReS₄(PtMe₂)₄] (Et₄N[4]), were characterized by ¹H, ¹³C, ¹⁹⁵Pt NMR spectroscopy and ESI mass spectrometry. The structure of Et₄N[1] was confirmed by single crystal X-ray diffraction, which demonstrated the expected square planar and tetrahedral coordination spheres bridged by a pair of sulfur atoms.     

Synthesis and structures of organoantimony compounds containing intramolecular Sb-N interactions

Stibines containing the pendant arm [2-(Me₂NCHR)C₆H₄] (where R = H or Me) were synthesized, and their reactions with CH3I and HBr have been carried out to obtain the diammonium salt {[2-(Me₂NCHR)C₆H₄] [2-(Me₃N⁺CHR)C₆H₄]}Sb 2[I]⁻ (where R = H 3; Me 4) and triammonium salt {2-[(Me₂HN⁺CH₂)C₆H₄]₃}Sb 3[Br]⁻5, respectively. A novel platinum complex 6 [PtCl₂ · 1] containing stibine 1 as a bidentate ligand has also been prepared. All these compounds show Sb-N interactions. A good conjunction was observed between semi-empirical method and ¹H and ¹³C NMR (at different temperature) data for the diammonium salts of compounds 3 and 4. The structures of all the synthesized compounds were determined by X-ray diffraction analyses. This appears to be the second molecular structure of a Pt stibine complex containing a Pt-Cl bond trans to stibine ligand, as few Pt-Sb X-ray structures are known.     

Synthesis and structure of bismuth complexes [Ph3MeP] 2 + [BiI3.5Br1.5(C5H5N)]2− · C5H5N, [Ph4Bi] 4 + [Bi4I16]4− · 2Me2C=O, and [Ph3(iso-Am)P] 4 + [Bi8I28]4− · 2Me2C=O

Complexes [Ph₃MeP] ₂ ⁺ [BiI_3.5Br_1.5(C₅H₅N)]^2? · C₅H₅N(I), [Ph₄Bi] ₄ ⁺ [Bi₄I₁₆]^4? · 2Me₂C=O (II), and [Ph₃(iso-Am)P] ₄ ⁺ [Bi₈I₂₈]^4? · 2Me₂C=O (III) were synthesized by reactions of bismuth iodide with triphenylmethylphosphonium bromide, triphenylbismuthonium sulfosalicylate, and triphenylisoamylphosphonium iodide, respectively. The crystal structures of complexes I–III were determined by X-ray crystallography. The complexes contain, in addition to cations and solvent molecules, mono-, tetra-, and octanuclear anions, in which bismuth atoms are in octahedral coordination.     

Reactions of P4S10 and pyPS2Cl with N,N′-diphenylurea and N,N′-diphenylthiourea

The reaction of P₄S₁₀ (1) with N,N′-diphenylurea (PhNH)₂CO (2) results in new heterocyclic compounds: the pyridinium salt of 1,3-diphenyl-2-sulfido-2-thioxo-1,3-diaza-2λ⁵-phosphetidine (3) (with a P–N–C–N cycle) and the pyridinium salt of 1,4-diphenyl-2,5-disulfido-2,5-dithioxo-1,4-dithiadiaza-2λ⁵,5λ⁵-diphosphinane (4), containing the (P–S–N)₂ cycle and the cyclic thiophosphates [pyH]₂[P₂S₈] (5), [pyH]₂[P₂S₇] (6) and [pyH]₃[P₃S₉] (7). A similar reaction, but carried out with N,N′-diphenylthiourea (PhNH)₂CS (8), leads to the formation of 4 and 6. pyPS₂Cl (9), used as an alternative starting material, also yields compounds 3, 4, 5, and further [pyH][PS₂Cl₂] (10) and S₈ after reaction with 2. Compound 3 reacts with Pd(CH₃COO)₂, with the formation of the complex [Pd(Ph₂N₂COPS₂)₂] (11). The crystal structures of 3 and 7 were determined by single-crystal X-ray diffraction.     

Synthesis and structure of antimony iodide complexes: [Ph3MeP] + 2 [SbI5]2−, [Ph3MeP] + 3 [Sb3I12]3−·Me2C=O, [Ph3MeP] + 3 [Sb3I12]3−, and [Ph3MeP] + 3 [Sb2I9]3−

Complexes with antimony-containing anions, [Ph₃MeP] ₊ ² [SbI₅]^2? (I), [Ph₃MeP] ₊ ² [Sb₃I₁₂]^3? (II), [Ph₃MeP] ₊ ³ [Sb₃I₁₂]^3? · Me₂C=O (III), and [Ph₃MeP] ₊ ³ [Sb₂I₉]^3? (IV), were synthesized by reacting triphenylmethylphosphonium iodide with antimony iodide. The central atom in the cations of the complexes has a distorted tetrahedral coordination. In the trinuclear anions of complexes II and III, each of the terminal SbI₃ groups is bound to the central Sb atom through two μ₂- and one μ₃ iodine bridges (SbSbSb angles are 103.0° and 102.2°, respectively). In the binuclear anion of complex IV, antimony atoms are linked with each other via three bridging iodine atoms.