Coupling insertion reactions of diphenylbuta-1, 4-diyne into iron-carbene bonds of [Fe2(CO)7{μ-C(Ph)C(NEt2}]. Syntheses and reactivities of the ferracyclopentadiene [Fe2(CO)6{C(Ph)C(NEt2)C(Ph)C(C2Ph)}] with [Fe2(CO)9]

The diiron ynamine complex [Fe₂(CO)₇{-C(Ph)C(NEt₂)}] (1) reacts with the diphenylbuta-1, 4-diyne, PhCC-CCPh, in refluxing hexane to yield three isomer complexes [Fe₂(CO)₆{C(Ph)C(NEt₂)C(Ph)C(C₂Ph}] (2a), [Fe₂(CO)₆{C(Ph)C(NEt₂)C(C₂Ph)C(Ph)}] (2b), and [Fe₂(CO)₆{NEt₂)C(Ph)C(C₂)C(Ph)}] (2c) All three compounds were identified by their¹H NMR spectra. Compounds2a and2c were characterized by single crystal X-ray diffraction analyses. Crystal data: for2a: space group = P2₁/n,a = 17.873(1) Å, = 18.388(6) Å,c = 9.429(3) Å = 91.99(3)°,Z = 4.3751 reflections,R = 0.044; for2c: space group = P2₁/n,a = 40.58(2) å,b = 12.101(9) Å,c = 12.551(5) Å, = 94.29(7)°,Z = 8.4723 reflection,R = 0.076. Complexes2a and2b result from a [2 + 2] cycloaddition between one of the CC triple bonds of the diyne ligand and the FeC carbene bond, whereas2c results from insertion of one of the CC group into the bridging carbene. Addition of [Fe₂(CO)₉] on2a gave two major products, the tripledecker [Fe₃(CO)₈{C(Ph)C(NEt₂)C(C₂Ph)}], (3 and a tetrairon cluster [Fe₄(CO)₁₁{C(Ph)C(NEt₂)C(Ph)C(C₂Ph)}] (4). Both compounds were characterized by single crystal diffraction analyses. Crystal data: for3: space group = P2₁/n,a = 12.039(3) Å,b = 18.046(3) å,c = 15.270(2) Å, = 90.11(2)°,Z = 4, 1430 reflections,R = 0.067; for4 space group = C2/c,a = 18.633(3) Å,b = 21.467(1)_Å,c = 20.742(2) Å, = 115.03(8)°,Z = 8.992 reflections, R = 0.076. Complex4 is based on a spiked triangular cluster with the alkynyl triple bond attached in ₃-parallel mode on the triangular grouping.     

Synthesis and structure of Bis(tetraphenylantimony) 1,2-diphenylethanedione dioximate toluene solvate Ph4SbONC(Ph)C(Ph)ONSbPh4 · 2PhCH3 and tetraphenylantimony 2-hydroxy-1,2-diphenylethanone oximate Ph4SbONC(Ph)CH(Ph)OH

Bis(tetraphenylantimony) 1,2-diphenylethanedione dioximate toluene solvate Ph₄SbONC(Ph)C(Ph)NOSbPh₄ · 2 PhCH₃ (I) and tetraphenylantimony 2-hydroxy-1,2-diphenyl(ethanone oximate Ph₄SbONC(Ph)CH(Ph)OH (II) have been synthesized by the reaction of pentaphenylantimony with 1,2-diphenylethane dioxime and 2-hydroxy-1,2-diphenylethanone oxime in toluene. A molecule of compound I is centrosymmetric with an inversion center at the midpoint of the C-C bond in the ethane moiety. A crystal of compound II contains two types of crystallographically independent molecules A and B. Antimony atoms in compounds I and II have a distorted tetragonal bipyramidal surrounding: equatorial CSbC and axial CSbO angles are 114.95(10)°–126.82(11)° and 173.24(9)° (I), 117.2(2)°–122.9(2)° and 178.15(18)° (IIA), and 112.3(2)°–127.7(2)° and 175.09(18)° (IIB), respectively. The Sb-C and Sb-O bond lengths are 2.106(3)–2.182(3) and 2.1344(17) ÅI), 2.118(5)–2.4199(5) and 2.153(4)Å(IIA), and 2.106(5)–2.200(5) and 2.120(4) Å (IIB), respectively. A molecule of compounds I, IIA, and IIB has been found to contain Sb...N intramolecular contacts (2.838(3), 2.867(5), and 2.889(5)Å, respectively). Molecules of compounds IIA and IIB contain O-H...N hydrogen bonds (H...N, 1.91(9) and 2.06(8) Å, respectively).     

Ring and Cluster Structures of {Li[C(NtBu)2(HNtBu)]}2·(THF) and {Li2[C(NtBu)3]}2, Containing the Novel Anions [C(NtBu)2(HNtBu)]−- and [C(NtBu)3]2−

The reaction of tert.-butyl carbodiimide with one equivalent of LiNH^tBu in tetrahydrofuran at-78 °C produces {Li[C(N^tBu)₂(HN^tBu)]}₂-(THF) (1), which is an eight-membered Li₂C₂N₄ ring; the deprotonation of (1) with two equivalents of n-BuLi in tetrahydrofuran at -78 °C and recrystallisation of the product from n-pentane yielded the unsolvated dimer {Li₂[C(N^tBu)₃]}₂ (2), which adopts the structure of a distorted hexagonal prism.     

Phosphido-phosphinidene transformations. Ru3(CO)6-[P(Ph)C(Ph)C(Ph)](μ-PPh2)2: A novel six vertex nido-pentagonal bipyramidal structure via reductive elimination and acetylene insertion at a triruthenium centre

The complex Ru₃(CO)₆[P(Ph)C(Ph)C(Ph)](μ-PPh₂)₂ has been obtained by treating (μ-H)Ru₃(CO)₇(μ-PPh₂)₃ with C₂Ph₂ in aliphatic hydrocarbons and its structure has been determined by an X-ray diffraction study. The alkyne inserts into a RuP bond and there is reductive elimination of benzene, formed by coupling of a phenyl group of the μ-PPh₂ ligand with the cluster μ-hydride.     

Synthesis and structure of the dimeric organo-antimony (V) imido complex [Ph3Sb(μ-NCH2CH2Ph)]2

The amine PhCH₂CH₂NH₂ undergoes dimetallation by [Ph₃Sb(NMe₂)₂] (1) under mild conditions to give the first structurally authenticated example of an organo-Sb(V) imido complex, [Ph₃Sb(μ-NCH₂CH₂Ph)]₂ (2).     

Synthesis and Characterisation of New Metallacycles Containing [Ph2P(E)NP(E)Ph2]− (E = S OR Se) Ligands

Abstract

Reaction of [Ph₂P(E)NP(E)Ph₂]^? (E = S or Se) with a series of late transition-metal dimers, in thf or MeOH, leads to facile bridge cleavage and formation of new mononuclear compounds.     

Synthesis and structure of bismuth-containing complexes [(Ph4BiO)2{2,5-(CH3)2C6H3S(O)}] 2 + [Ph2Bi2I6]2−,[(Ph4Bi]+[PhBi(C5H5N)I3]−, [Ph4Sb] 4 + [Bi4I16]4−⋅2(CH3)2 C=O, and [Ph4Sb] 3 + [Bi5I18]3−

The reactions of tetraphenylbismuthonium and -stibonium salts Ph₄EX (E = Bi, Sb; X = I, OSO₂ (C₆H₃(CH₃)₂-2,5), OSO₂C₆H₃(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes [Ph₄Bi]⁺[PhBi(C₅H₅N)I₃]^-, [(Ph₄BiO)₂S(O){2,5-(CH₃)₂C₆H₃S(O)} [Ph₂Bi₂I₆]^2–, [Ph₄Sb [Bi₄I₁₆]^4-·2(CH₃)²C=O, and [Ph₄Sb] ₃₊ ⁺ [Bi₅I₁₈]^3-, whose structural units, according to the X-ray diffraction data, are tetraphenylbismuthonium (-stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively.     

(C60)2Ru2Cl4[Ph2P(CH2)4PPh2]配合物的合成

在氮气氛中采用配体取代法合成了C60以σ-π配位方式与Ru形成的稳定η2型富勒烯双核钌金属配合物(C60)2Ru2Cl4[Ph2P(CH2)4PPh2],其结构经UV,IR,XPS,XRD和元素分析表征.     

Lanthanide nitrate complexes of diphenylmethylphosphine oxide: synthesis and spectroscopic studies. Crystal structures of [La(Ph2MePO)3(NO3)3], [La(Ph2MePO)4(NO3)3]·xMe2CO and [Yb(Ph2MePO)4(NO3)2]PF6

The reaction of Ln(NO₃)₃·6H₂O (Ln=lanthanide except Pm) with Ph₂MePO in a 1:3 or 1:4 ratio in acetone or ethanol produces [Ln(Ph₂MePO)₃(NO₃)₃] which have been characterised by analysis, IR, ¹H and ³¹P{¹H} NMR spectroscopy and conductance measurements. The [Ln′(Ph₂MePO)₃(NO₃)₃] (Ln′=Pr–Tb) exist only as tris complexes in solution and are unaffected by the presence of excess Ph₂MePO. In contrast the [Ln″(Ph₂MePO)₃(NO₃)₃] (Ln″=Ho–Lu) partially decompose in CH₂Cl₂ solution into [Ln″(Ph₂MePO)₄(NO₃)₂]⁺, and [Ln″(Ph₂MePO)₄(NO₃)₂]PF₆ are readily isolated from Ln″(NO₃)₃, Ph₂MePO and NH₄PF₆ in acetone. For lanthanum only, a neutral 1:4 complex [La(Ph₂MePO)₄(NO₃)₃] was isolated. X-ray crystal structures show that [La(Ph₂MePO)₃(NO₃)₃] contains nine-coordinate La, whilst [La(Ph₂MePO)₄(NO₃)₃]·xMe₂CO contains a ten-coordinate metal centre. The structure of [Yb(Ph₂MePO)₄(NO₃)₂]PF₆ reveals an eight-coordinate cation and all complexes contain bidentate nitrato-groups.     

Fixation and reduction of molecular nitrogen by [WH4(PC2H5Ph2)4] and [WH4(PCH3Ph2)4] in a γ-radiation field

Hydride complexes of W(IV) with dpep (diphenylethylphosphine) and dpmp (diphenylmethylphosphine) were irradiated in thf+C₆H₁₂(11) solutions, saturated with N₂+H₂(13). Radiation yields of hydrazine, ammonia and amines were evaluated. The mechanism of reduction of molecular nitrogen is discussed.     

Synthesis and structure of gold complexes [Ph3PR]+[Au(CN)2I2-trans]−, R = Et,CH2Ph,Ph

Russian Chemical Bulletin - Gold complexes [Ph3PR]+[Au(CN)2I2-trans]?, where R = Et (1), CH2Ph (2), Ph (3), were synthesized by the reaction of potassium dicyanodiiodoaurate with...     

Structurally different divalent metallasiloxanes [Mg{O(Ph2SiO)2}2]-μ-(LiPy)-μ-{(LiPy)3(OH)(Cl)}], [Cr{O(Ph2SiO)2}-μ-(LiPy2)2], and [{O(Ph2SiO)2}Co{O(Ph2SiO)3)}-μ-(LiPy2)2] from Ph2Si(OH)2/2BuLi and the metal dichlorides

Three structurally different metallasiloxanes were formed from reactions between in situ generated suspensions of Ph₂Si(OH)₂/BuLi (1∶2) in tetrahydrofuran (THF) with, metal dichlorides MgCl₂·2THF, CrCl₂, or CoCl₂ followed by toluene/Py (Py=pyridine) work-up. The X-ray structures are reported for: [Mg{O(Ph₂SiO)₂}₂]-μ-(LiPy)-μ-{(LiPy)₃(OH)(Cl)] (1) incorporating two six-membered magnesiasiloxane rings and an MgLi₃O₃Cl cubane fragment, [{O(Ph₂SiO)₂}Co{O(Ph₂SiO)₃}-μ-(LiPy₂)₂] (2) with both six-and eight-membered cobaltasiloxane rings and [Cr{O(Ph₂SiO)₂}₂-μ-(LiPy₂)₂] (3) with two six-membered chromiasiloxane rings. Structure assembly in these cases is apparently dictated by the metal dichloride. The compound [{O(Ph₂SiO)₂}Mg{O(Ph₂SiO)₃}-μ-(CoClPy)₂]·Py (4) is formed from [{O(Ph₂SiO)₂}Mg{O(Ph₂SiO)₃}-μ-(LiPy₂)₂] and CoCl₂ (1∶2).     

Synthesis and structures of mercury and cadmium complexes: [Ph4Sb] 2 + [Hg2I6]2−·Ph2Hg, [Ph4Sb] 2 + [E2I6]2− (E = Hg, Cd), and [Ph4Sb] 2 + [Hg4I10]2−

The reaction of pentaphenylantimony with mercury iodide affords the ionic complex [Ph₄Sb] ₂ ⁺ [Hg₂I₆]^2?·Ph₂Hg (I). The [Ph₄Sb] ₂ ⁺ [Hg₂I₆]^2? (II) and [Ph₄Sb] ₂ ⁺ [Cd₂I₆]^2? (III) complexes are synthesized from tetraphenylantimony iodide and mercury and cadmium iodides. The [Ph₄Sb] ₂ ⁺ [Hg₄I₁₀]^2? complex (IV) is prepared from tetraphenylantimony 2,4-dimethylbenzenesulfonate and mercury iodide. According to the X-ray diffraction data, the Sb atom in the [Ph₄Sb]⁺ cations of complex I has virtually ideal tetrahedral coordination (the CSbC angles are 108.09°–109.64°). In the central square fragment Hg₂I₂ of the [Hg₂I₆]^2? anion, the Hg-I_br bond lengths are 2.825 and 3.075 Å, and the terminal iodine atoms are more strongly bonded to the mercury atoms (Hg-I_term 2.691 and 2.700 Å). The [Cd₂I₆]^2? anion in complex III has a similar structure (the Cd-I_bridg and Cd-I_term distances are 2.865, 2.872 and 2.723, 2.748 Å, respectively). The anions in complex IV are joined by I…Hg (3.651 Å) and I…I (4.058 Å) interactions into an infinite dimeric network.     

Methyl Propiolate Cluster Complex (Ph4P)2[W6I8(C≡C–C(O)OCH3)6]

Russian Journal of Coordination Chemistry - A new organometallic iodide cluster complex (Bu4N)2[W6I8(C≡C–C(O)OCH3)6] (I), analogous to the previously described...     

Synthesis and crystal structure of [MoH3(CCBut)(Ph2PCH2CH2PPh2)2], a trihydrido-alkynyl complex

Reaction of Bu^tCCH with trans-[Mo(N₂)₂(dppe)₂] (dppe = Ph₂PCH₂CH₂PPh₂) gives [MoH₃(CCBu^t)(dppe)₂], whose X-ray structure is reported.     

Uranium versus Thorium: Synthesis and Reactivity of [η5-1,2,4-(Me3C)3C5H2]2U[η2-C2Ph2]

The synthesis, electronic structure, and reactivity of a uranium metallacyclopropene were comprehensively studied. Addition of diphenylacetylene (PhC≡CPh) to the uranium phosphinidene metallocene [η⁵-1,2,4-(Me₃C)₃C₅H₂]₂U=P-2,4,6-tBu₃C₆H₂ ( 1 ) yields the stable uranium metallacyclopropene, [η⁵-1,2,4-(Me₃C)₃C₅H₂]₂U[η²-C₂Ph₂] ( 2 ). Based on density functional theory (DFT) results the 5f orbital contributions to the bonding within the metallacyclopropene U-(η²-C=C) moiety increases significantly compared to the related Th^IV compound [η⁵-1,2,4-(Me₃C)₃C₅H₂]₂Th[η²-C₂Ph₂], which also results in more covalent bonds between the [η⁵-1,2,4-(Me₃C)₃C₅H₂]₂U²⁺ and [η²-C₂Ph₂]²⁻ fragments. Although the thorium and uranium complexes are structurally closely related, different reaction patterns are therefore observed. For example, 2 reacts as a masked synthon for the low-valent uranium(II) metallocene [η⁵-1,2,4-(Me₃C)₃C₅H₂]₂U^II when reacted with Ph₂E₂ (E=S, Se), alkynes and a variety of hetero-unsaturated molecules such as imines, ketazine, bipy, nitriles, organic azides, and azo derivatives. In contrast, five-membered metallaheterocycles are accessible when 2 is treated with isothiocyanate, aldehydes, and ketones.     

The synthesis of platinum and palladium cluster compounds with isocyanide or functionalised phosphine ligands. Crystal structures of [Pt5(CO)(μ-CO)5{Ph2PCH2C(O) Ph}4 and [Pt5(μ-CNC6H3Me2-2, 6)3(CNC6H3Me2-2, 6)5 {Ph2PCH2C(O) Ph}2]

The reaction of the ketophosphine ligand Ph₂PCH₂C(O)Ph (P～O) with [PtCl₂(NCMe)₂] and carbon monoxide in THF in the presence of an excess of zinc afforded the 70 electron pentanuclear cluster [Pt₅(CO)(μ-CO)₅(P～O)₄] (1). Reaction of the palladium(0) complex [Pd₂(dba)₃] CHCl₃ (dba = dibenzylideneacetone) with Ph₂PCH₂C(O)R [R = Ph or C₅H₄Fe(C₅H₅)] under SO₂ led to the pentapalladium cluster compounds [Pd₅(μ₃-SO₂)₂ (μ-SO₂)₂ {Ph₂PCH₂C(O)R}₅] (2a,R = Ph;2b,R = C₅H₄Fe(C₅H₅)), Cluster (1) reacts with 2,6-xylyl isocyanide, CNC₆H₃Me₂-2,6 to give a red cluster of formula [Pt₅(μ-CNC₆H₃Me₂-2, 6)₃ (CNC₆H₃Me₂-2, 6)₅ (P～O)₂] (3) and a green complex (4). The corresponding complexes (6) and (7) were also obtained by using PPh₃ instead of P～O. Clusters (2a) and (2b) react with [NEt₃Bz] Cl to give[NEt₃Bz][Pd₃(μ-SO₂)₂ (μ-Cl){Ph₂PCH₂C(O)R}₃](8a,R = Ph;8b,R = C₅H₄Fe(C₅H₅)). The molecular structures of (1) and (3) were determined by single-crystal X-ray diffraction analyses.     

Investigating the role of the outer-coordination sphere in [Ni(P(Ph)2N(Ph‑R)2)2]2+ hydrogenase mimics

A series of dipeptide substituted nickel complexes with the general formula, [Ni(P(Ph)(2)N(NNA-amino acid/ester)(2))(2)](BF(4))(2), have been synthesized and characterized (P(2)N(2) = 1,5-diaza-3,7-diphosphacyclooctane, and the dipeptide consists of the non-natural amino acid, 3-(4-aminophenyl)propionic acid (NNA), coupled to amino acid/esters = glutamic acid, alanine, lysine, and aspartic acid). Each of these complexes is an active electrocatalyst for H(2) production. The effects of the outer-coordination sphere on the catalytic activity for the production of H(2) were investigated; specifically, the impact of sterics, the ability of the side chain or backbone to protonate and the pK(a) values of the amino acid side chains were studied by varying the amino acids in the dipeptide. The catalytic rates of the different dipeptide substituted nickel complexes varied by over an order of magnitude. The amino acid derivatives display the fastest rates, while esterification of the terminal carboxylic acids and side chains resulted in a decrease in the catalytic rate by 50-70%, implicating a significant role of protonated sites in the outer-coordination sphere on catalytic activity. For both the amino acid and ester derivatives, the complexes with the largest substituents display the fastest rates, indicating that catalytic activity is not hindered by steric bulk. These studies demonstrate the significant contribution that the outer-coordination sphere can have in tuning the catalytic activity of small molecule hydrogenase mimics.     

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.