Synthesis and properties of alkaline metal complexes with new overcrowded β-diketiminato ligands

Enaminoimines TbtNHC(Me)CHC(Me)NAr (5, Tbt = 2,4,6-[CH(SiMe₃)₂]₃C₆H₂) bearing a Tbt group were synthesized by the two steps condensation of acetylacetone with bulky amines. Enaminoimines 5 were treated with n-BuLi to give the corresponding lithium β-diketiminates, [Li{TbtNHC(Me)CHC(Me)NAr}] (1). The X-ray structural analysis of [Li{TbtNC(Me)CHC(Me)NMes}] (1c, Mes = mesityl) revealed that it is a monomeric, solvent-free lithium β-diketiminate. The equilibrium between free 1c plus THF and THF-coordinated (1c · thf) was investigated in detail by the determination of the association constant (K_a) in C₆D₆ at 293 K and the Job’s plot. The heavier alkali metal complexes, sodium and potassium β-diketiminates (6c–9c), were prepared by the two routes. THF-coordinated [M{TbtNC(Me)CHC(Me)NMes}(thf)] (6c: M = Na. 7c: M = K) were prepared by the reaction of 5c (Ar = Mes) with MH (M = Na, K). Solvent-free [M{TbtNC(Me)CHC(Me)NMes}] (8c: M = Na. 9c: M = K) were prepared by the reaction of 1c with t-BuOM (M = Na, K).     

Reactivity of intramolecularly coordinated aluminum compounds to R3EOH (E = Sn,Si). Remarkable migration of N,C,N and O,C,O pincer ligands

The reaction of organoaluminum compounds containing O,C,O or N,C,N chelating (so called pincer) ligands [2,6-(YCH₂)₂C₆H₃]AlⁱBu₂ (Y = MeO 1, ^tBuO 2, Me₂N 3) with R₃SnOH (R = Ph or Me) gives tetraorganotin complexes [2,6-(YCH₂)₂C₆H₃]SnR₃ (Y = MeO, R = Ph 4, Y = MeO, R = Me 5; Y = ^tBuO, R = Ph 6, Y = ^tBuO, R = Me 7; Y = Me₂N, R = Ph 8, Y = Me₂N, R = Me 9) as the result of migration of O,C,O or N,C,N pincer ligands from aluminum to tin atom. Reaction of 1 and 2 with (ⁿBu₃Sn)₂O proceeded in similar fashion resulting in 10 and 11 ([2,6-(YCH₂)₂C₆H₃]SnⁿBu₃, Y = MeO 10; Y = ^tBuO 11) in mixture with ⁿBu₃SnⁱBu. The reaction 1 and 3 with 2 equiv. of Ph₃SiOH followed another reaction path and ([2,6-(YCH₂)₂C₆H₃]Al(OSiPh₃)₂, Y = MeO 12, Me₂N 13) were observed as the products of alkane elimination. The organotin derivatives 4–11 were characterized by the help of elemental analysis, ESI-MS technique, ¹H, ¹³C, ¹¹⁹Sn NMR spectroscopy and in the case 6 and 8 by single crystal X-ray diffraction (XRD). Compounds 12 and 13 were identified using elemental analysis,¹H, ¹³C, ²⁹Si NMR and IR spectroscopy.     

Heat capacities and derived thermodynamic properties of lithium,sodium, and potassium disilicates from T = (5 to 350) K in both vitreous and crystalline states

Cryogenic heat capacities determined by equilibrium adiabatic calorimetry from T = (6 to 350) K on Li, Na, and K disilicates in both crystalline and vitreous phases are adjusted to end member composition and the vitreous/crystal difference ascertained. The thermophysical properties of these and related phases are estimated, compared, and updated. The values at T = 298.15 K of {S^∘(T) − S^∘(0)}/R for stoichiometric compositions of alkali disilicate (M₂O · 2SiO₂): vitreous, crystal: Li, 16.30, 14.65; Na, 20.67, 19.47; and K, 23.26, 23.00. Entropy differences confirm greater disorder in the vitreous compounds compared with the crystalline compounds. The entropy data also show that disorder increases with decreasing atomic mass of the alkali ion.     

[MoFe3S4]3+ and [MoFe3S4]2+ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety

A series of organometallic molybdenum/iron/sulfur clusters of the general formula [Cp¹MoFe₃S₄L_n]^m (Cp¹ = η⁵-C₅Me₅; L = S^tBu, SPh, Cl, I, n = 3, m = 1−; L_n = I₂(P^tBu₃), m = 0; L = 2,6-diisopropylphenylisocyanide (ArNC), n = 7, m = 1+) have been synthesized. A cubane cluster (PPh₄)[Cp¹MoFe₃S₄(S^tBu)₃] (2) was isolated from a self-assembly reaction of Cp¹Mo(S^tBu)₃ (1), FeCl₃, LiS^tBu, and S₈ followed by cation exchange with PPh₄Br in CH₃CN, while an analogous cluster (PPh₄)[Cp¹MoFe₃S₄(SPh)₃] (3) was obtained from the Cp¹MoCl₄/FeCl₃/LiSPh/PPh₄Br reaction system or from a ligand substitution reaction of 2 with PhSH. Treatment of 2 with benzoyl chloride gave rise to (PPh₄)[Cp¹MoFe₃S₄Cl₃] (4), which was in turn converted to (PPh₄)[Cp¹MoFe₃S₄I₃] (5) by the reaction with NaI. A neutral cubane cluster Cp¹MoFe₃S₄I₂(P^tBu₃) (6) was generated upon treating 5 with P^tBu₃. Although reduction of 4 by cobaltocene under the presence of ArNC resulted in a disproportionation of the cubane core to give Fe₄S₄(ArNC)₉Cl (7), a similar reduction reaction of 5 produced [Cp¹MoFe₃S₄(ArNC)₇]I (8), where the MoFe₃S₄ core was retained. The crystal structures of 4–6, and 8 were determined by the X-ray analysis.     

Activation of C–H bonds of hydrocarbons by the ArH–alkali metal systems in THF (ArH – naphthalene,biphenyl, anthracene,phenanthrene, trans-stilbene,pyrene). Alkylation of naphthalene and toluene with ethene

Systems based on naphthalene and alkali metals (Li, Na, K) in THF are able to induce the alkylation of naphthalene with ethene at room temperature and atmospheric pressure. The highest activity in this reaction is exhibited by the naphthalene–potassium system which converts naphthalene into 1-ethylnaphthalene (1) and small amounts of two isomeric dihydro derivatives of 1 in a yield of 85% (24 h, K:C₁₀H₈ = 2:1). The same alkylation products are formed when metallic sodium is used instead of potassium. The interaction of ethene with the naphthalene–lithium system (24 h, Li:C₁₀H₈ = 2:1) affords 1 together with 1-n-butylnaphthalene (4), 1-n-hexylnaphthalene (5), 1-n-oktylnaphthalene (6) and dihydro derivatives of 5 and 6 in a total yield of 60%. Alkylation of toluene with ethene in the naphthalene–alkali metal systems leads to the formation of higher monoalkylbenzenes. The greatest toluene conversion (48%, 24 h) is observed on using the lithium-containing system (Li:C₁₀H₈ = 2:1), in the presence of which a mixture of n-propylbenzene (11), n-pentylbenzene (12), 3-phenylpentane (13) and 3-phenylheptane (14) is produced from ethene and toluene. On the replacement of lithium by sodium or potassium, only 11 and 13 are obtained. A treatment of biphenyl, phenanthrene, trans-stilbene, pyrene and anthracene with alkali metals in THF also gives systems capable of catalyzing the alkylation of toluene with ethene at 22 °C. Of particularly active is the stilbene–lithium system (Li:stilbene = 3:1) which converts toluene into a mixture of 11–14, n-heptylbenzene and 5-phenylnonane in a yield of 58%. In all cases, the rate of the alkylation considerably increases in the presence of the solid phase of alkali metal. The mechanism of the reactions found is discussed.     

Long-distance electronic interaction in a molecular wire consisting of a ferrocenyl–ethynyl unit bridging two [(η5-C5H5)(dppe)M] metal centers

Several multinuclear ferrocenyl–ethynyl complexes of formula [(η⁵-C₅H₅)(dppe)M^II?CC–(fc)_n–CC–M^II(dppe)(η⁵-C₅H₅)] (fc = ferrocenyl; dppe = Ph₂PCH₂CH₂PPh₂; 1: M^II = Ru²⁺, n = 1; 2: M^II = Ru²⁺, n = 2; 3: M^II = Ru²⁺, n = 3; 4: M^II = Fe²⁺, n = 2; 5: M^II = Fe²⁺, n = 3) were studied. Structural determinations of 2 and 4 confirm the ferrocenyl group directly linked to the ethynyl linkage which is linked to the pseudo-octahedral [(η⁵-C₅H₅)(dppe)M] metal center. Complexes of 1–5 undergo sequential reversible oxidation events from 0.0 V to 1.0 V referred to the Ag/AgCl electrode in anhydrous CH₂Cl₂ solution and the low-potential waves have been assigned to the end-capped metallic centers. The solid-state and solution-state electronic configurations in the resulting oxidation products of [1]⁺ and [2]²⁺ were characterized by IR, X-band EPR spectroscopy, and UV–Vis at room temperature and 77 K. In [1]⁺ and [2]²⁺, broad intervalence transition band near 1600 nm is assigned to the intervalence transition involving photo-induced electron transfer between the Ru³⁺ and Fe²⁺ metal centers, indicating the existence of strong metal-to-metal interaction. Application of Hush’s theoretical analysis of intervalence transition band to determine the nature and magnitude of the electronic coupling between the metal sites in complexes [1]⁺ and [2]²⁺ is also reported. Computational calculations reveal that the ferrocenyl–ethynyl-based orbitals do mix significantly with the (η⁵-C₅H₅)(dppe)Ru metallic orbitals. It clearly appears from this work that the ferrocenyl–ethynyl spacers strongly contribute in propagating electron delocalization.     

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

In this review, the synthesis, reactivity and properties of linear and cyclic oligophosphanides are described. Specifically the structures and versatile reactivity of the anionic ligands (P₄R₄)^2? (R = Bu^t, Ph, Mes), (P₄HR₄)^? (R = Ph and Mes) and cyclo-(P₅Bu^t₄)^? towards main group and transition metal complexes is elucidated. In addition, potential application of metal oligophosphanides as precursors for the preparation of metal phosphides is also briefly discussed.     

Synthesis and characterization of novel intramolecularly O,C,O-coordinated heteroleptic organostannylenes and their tungstenpentacarbonyl complexes

The syntheses are reported of the novel heteroleptic organostannylenes [2,6-(ROCH₂)₂C₆H₃]SnCl (1, R = Me; 2, R = t-Bu) and of their tungstenpentacarbonyl complexes [2,6-(ROCH₂)₂C₆H₃](X)SnW(CO)₅ (3, X = Cl, R = Me; 4, X = Cl, R = t-Bu; 5, X = H, R = Me). The compounds were characterized by means of elemental analyses, ¹H, ¹³C, ¹¹⁹Sn NMR spectroscopies, electrospray mass spectrometry and in case of 3 and 4 also by single crystal X-ray diffraction analysis. For the two latter compounds the substituents bound at the ether oxygen atom control the strength of intramolecular O → Sn coordination. Thus, the O–Sn distances amount to 2.391(5)/2.389(5) (3) and 2.464(3)/2.513(3) Å (4).     

Stereospecific polymerization of propylene with group 4 ansa-fluorenylamidodimethyl complexes

Group 4 [η¹:η³-tert-butyl(dimethylfluorenylsilyl)amido]dimethyl complexes [t-BuNSiMe₂Flu]MMe₂ (M = Ti, 1; Zr, 2; Hf, 3) were synthesized in a one-pot synthesis starting from the ligand, MeLi and MCl₄ (M = Ti, Zr, Hf), respectively. The structures of these complexes were determined by X-ray crystallography and the results obtained revealed that the fluorenyl ligand coordinates to center metal in a η³-manner irrespective of center metal employed. Propylene polymerization was conducted at 0 or 20 °C in toluene by 1–3 combined with dried methylaluminoxane (MAO), which was prepared from the toluene solutions of MAO by removing free trialkylaluminiums, and HNMe₂PhB(C₆F₅)₄ in the presence of triisobutylaluminium. The 1–dried MAO system gave the polymer with syndiotactic triad (rr) of 63% at 0 °C, whereas 2 and 3 did not give any polymer in the same conditions. The 2–dried MAO system gave the polymer with the highest syndiotacticity (rr = 97%) at 20 °C, although the activity was low. The 3–dried MAO system did not give any polymer even at 20 °C. When HNMe₂PhB(C₆F₅)₄ was used in place of dried MAO at 20 °C, 1 gave almost atactic polymer, while 2 and 3 gave highly syndiotactic one (rr > 90%). These results indicate that the catalytic performance strongly depended on the center metal of the ansa-fluorenylamidodimethyl complexes as well as cocatalysts employed.     

Crucial effect of rubidium cation on catalytic activity of a polycrystalline gold electrode toward oxygen reduction reaction in alkaline media

Catalytic activity of a polycrystalline gold electrode toward oxygen reduction reaction (ORR) in aqueous alkaline media in the presence of various alkali-metal sulfates (M₂SO₄, M = Li, Na, K, Rb and Cs) was investigated by hydrodynamic voltammetry. The fraction of 4e^? pathway in low overpotentials (? 0.1 to ? 0.3 V) depended on the alkali-metal cations (Rb ? Na, K, Cs, Li). A complete 4e^? reduction of O₂ was only attained in the presence of Rb⁺ cation in the solution, which was comparable or even superior to that reported at the Au(100) single crystal electrode.     

Structure and magnetic properties of 3-oxyl-4,4,5,5-tetramethyl-2-oxoimidazolidin-1-olates

The paramagnetic salts (NH₃Bu^t)1 and [K(NH₂Bu^t)₂]1, where 1 is the 3-oxyl-4,4,5,5-tetramethyl-2-oxoimidazolidin-1-olate anion, were isolated for the first time in the individual state. The crystal structure of [K(NH₂Bu^t)₂]1 involves polymer chains formed by hydrogen bonding between anions 1 and [K₂(NH₂Bu^t)₄]²⁺ cation dimer fragments. The magnetic properties of [K(NH₂Bu^t)₂]1 are well described by the quasi-isolated dimer model with spins S = 1/2 coupled by weak exchange interactions via [K₂(NH₂Bu^t)₄]² fragments in polymer chains.     

Metal–metal bond cleavage of carbene complexes by halogens: The crystal and molecular structures of ax-[Mn2(CO)9{C(OEt)2-thienyl}], [Mn(CO)4(I){C(OEt)2-thienyl}] and eq-[Mn2(CO)9{C(NH2)2-thienyl}]

The metal–metal bond in [M₂(CO)₉{C(OEt)R}] (M = Mn (1), Re (2), R = 2-thienyl (a), 2-bithienyl (b)) is readily cleaved with halogens to afford cis-[M(CO)₄(X){C(OEt)R}] (M = Mn (3), X = I; M = Re (4), X = Br). In the binuclear manganese complex, the carbene ligand is found in an axial position due to steric reasons, whereas the electronically favoured equatorial position is found for the carbene ligands in the corresponding rhenium complexes and in [Mn₂(CO)₉{C(NH₂)thienyl}] (5a), containing a sterically less demanding NH₂-substituent.     

The reaction of amidinato(pyridine) complexes of molybdenum and tungsten with triethylborane adduct of N-heterocyclic carbene (NHC · BEt3): Investigation on the reactivity of NHC · BEt3 as carbene precursor toward transition metal complexes

The reaction of triethylborane adduct of N-heterocyclic carbene, NHC · BEt₃, (NHC = IⁱPr = 1,3-diisopropylimidazol-2-ylidene (IⁱPr · BEt₃; 1a), NHC = IMes = 1,3-dimesitylimidazol-2-ylidene (IMes · BEt₃; 1b)), which was prepared by the reaction of the corresponding imidazolium salt with one equivalent of LiBEt₃H, with amidinato(pyridine) complex, [M(η³-allyl){η²-(NPh)₂CH}(CO)₂(NC₅H₅)] (M = Mo; 2-Mo M = W; 2-W), was investigated. The reaction of compound 1 with complex 2 under toluene-reflux conditions resulted in the formation of carbene complex [M(η³-allyl){η²-(NPh)₂CH}(CO)₂(NHC)] (M = Mo, NHC = IⁱPr; 3a-Mo, M = Mo, NHC = IMes; 3b-Mo, M = W, NHC = IⁱPr; 3a-W, M = W, NHC = IMes; 3b-W). These complexes were characterized spectroscopically as well as by X-ray analyses. Complex 3a-Mo was formed in various solvents such as 1,2-dimethoxyethane (DME), 1,2-dichloroethane, and acetonitrile under refluxing conditions for 3 h. In toluene, 3a-Mo was obtained in a good yield by heating at 70 °C for only 20 min. Employment of NHC · BEt₃ (1) was found to afford convenient route for the introduction of the carbene ligand to the transition metal complexes.     

Novel inorganic ionic liquids possessing low melting temperatures and wide electrochemical windows: Binary mixtures of alkali bis(fluorosulfonyl)amides

Thermal properties of alkali bis(fluorosulfonyl)amides, MFSI (M = Li, Na, K, Rb, Cs), have been investigated. Binary phase diagrams of LiFSI–KFSI and NaFSI–KFSI systems have been constructed. Eutectic point for LiFSI–KFSI is 338 K at (x_Li, x_K) = (0.45, 0.55) and, that for NaFSI–KFSI is 330 K at (x_Na, x_K) = (0.45, 0.55). The electrochemical window of the eutectic LiFSI–KFSI is as wide as 6.0 V at 348 K with the cathode limit being lithium metal deposition. The electrochemical window of the eutectic NaFSI–KFSI is 5.0 V at 340 K with sodium metal deposition at the cathode limit. These new inorganic ionic liquids are highly promising for various electrochemical applications.     

Crystal structures and magnetic properties of complexes of M(NO3)2; M = MnII,CoII, NiII,and CuII,with pyridine ligands carrying an aminoxyl radical

Four complexes of M(NO₃)₂(4NOPy-OMe)₂, (4NOPy-OMe = 4-(N-tert-butyloxylamino)-2-(methoxymethylenyl)pyridine, and M = Mn^II, 1; Co^II, 2; Ni^II, 3; Cu^II, 4), were prepared and fully characterized. X-ray single crystal analysis reveals that four complexes are isostructural. The molecular structures are distorted octahedral in which the methoxy oxygen atoms coordinate to the metal ion by trans-configuration while the pyridyl nitrogen atoms and the nitrate oxygen atoms coordinate by cis-configuration. The magnetic properties of all complexes were investigated by SQUID magneto/susceptometry. Temperature dependence of the molar magnetic susceptibilities in the temperature range of 2–300 K indicated that the magnetic coupling between aminoxyl radicals and metal ion was antiferromagnetic in the complex 1 and were ferromagnetic in the complexes 2–4. The quantitative analysis based on the spin Hamiltonian, H = −2J(S₁S_M + S_MS₂) yielded the best fit as J/k_B = −13.4 ± 0.1 K, g = 1.94 ± 0.002, and θ = −0.78 ± 0.02 K for the complex 1, J/k_B = 48.7 ± 2.1 K, g = 2.07 ± 0.02, and θ = −2.83 ± 0.41 K for the complex 3 (the data in the temperature range 300–50 K were used), and J/k_B = 57.0 ± 1.2 K, g = 2.002 ± 0.004, and θ = −9.8 ± 0.1 K for the complex 4.     

Organo-aluminum,zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP(NHtBu)3

Reactions of (^tBuHN)₃PNSiMe₃ (1) with the alkyl-metal reagents dimethylzinc, trimethylaluminum and di-n-butylmagnesium yield the monodeprotonated complexes [MeZn{(N^tBu)(NSiMe₃)P(NH^tBu)₂}] (2), [Me₂Al{(N^tBu)(NSiMe₃)P(NH^tBu)₂}] (3) and [Mg{(N^tBu)(NSiMe₃)P(NH^tBu)₂}₂] (4), respectively. Attempts to further deprotonate complex 2 with n-butyllithium or di-n-butylmagnesium result in nucleophilic displacement of the methylzinc fragment by lithium or magnesium. The two remaining amino protons of 3 are removed by reaction with di-n-butylmagnesium to give a heterobimetallic complex in which the coordination sphere of magnesium is completed by two molecules of THF (5 · 2THF) or one molecule of TMEDA (5 · TMEDA). Reaction of complex 3 with 1 equiv. of n-butyllithium followed by treatment of the product with di-n-butylmagnesium yields the complex {Me₂Al[(N^tBu)(NSiMe₃)P(N^tBu)₂]MgBu} Li · 4THF (6 · 4THF), the first example of a triply deprotonated complex of 1 containing three different metals. Reaction of complex 5 with iodine results in cleavage of an Al–Me group to give {MeIAl[(N^tBu)(NSiMe₃)P(N^tBu)₂Mg]} (7). Complexes 5 · 2THF, 5 · TMEDA, 6 · 4THF and 7 have been characterized in solution by multinuclear (¹H, ¹³C, ³¹P and ⁷Li) NMR spectroscopy, while the solid-state structures of 2, 4 and 5 · 2THF have been determined by X-ray crystallography.     

Dialkyl- and diaryl-platinum(II) complexes with secondary phosphines: Preparation,structure and thermal reaction giving the metallopolymer

Alkyl and arylplatinum complexes with 1,5-cyclooctadiene ligand, [PtR₂(cod)] (R = Me, Ph, C₆H₄-p-CF₃, C₆F₅), react with secondary phosphines, PHR′₂ (R′ = i-Bu, t-Bu, Ph), to afford the mononuclear platinum complexes, cis-[PtR₂(PHR′₂)₂] (1a: R = Me, R′ = i-Bu; 1b: R = Me, R′ = t-Bu; 1c: R = Me, R′ = Ph; 2a: R = Ph, R′ = i-Bu; 2b: R = Ph, R′ = t-Bu; 2c: R = R′ = Ph; 3a: R = C₆H₄-p-CF₃, R′ = i-Bu; 3b: R = C₆H₄-p-CF₃, R′ = t-Bu; 3c: R = C₆H₄-p-CF₃, R′ = Ph; 4a: R = C₆F₅, R′ = i-Bu; 4c: R = C₆F₅, R′ = Ph) in 81–98% yields. Molecular structures of the complexes except for 1a, 1c and 2a were determined by X-ray crystallography. Complex 1b has a square-planar structure with Pt–C(methyl) bonds of 2.083(8) and 2.109(8) Å, while the Pt–C(aryl) bonds of 2b–c, 3a–c, 4a and 4c (2.055(1)–2.073(8) Å) are shorter than them. Thermal decomposition of 1b, 2a–c, and 3a–c releases methane, biphenyl or 4,4′-bis(trifluoromethyl)biphenyl as the organic products, which are characterized by NMR spectroscopy. The solid product of the thermal reactions of 2b and 2c were characterized as the metallopolymers formulated as [Pt(PR′₂)₂]_n (5b: R′ = ^tBu; 5c: R′ = Ph), based on the solid-state NMR and elemental analyses.     

Synthesis of new substituted benzaldazine derivatives,hydrogen bonding-induced supramolecular structures and luminescent properties

Syntheses of three benzaldazine compounds 1–3 with the general formula Ar₁(CH = N–N = HC)Ar₂ (Ar₁ = Ar₂ = 2-OH-3,5-^tBu₂C₆H₂ (1), Ar₁ = Ar₂ = 2-BrC₆H₄ (2), Ar₁ = ortho-C₆H₄(NHC₆H₃-Me₂-2,6), Ar₂ = C₆H₄F-2 (3)) are described. All compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, IR spectroscopy and single-crystal X-ray crystallography. The different supramolecular structures were obtained through different weak interactions (C ? H···O, O ? H···N and π···π interactions for 1; C ? H···Br and Br···Br interactions for 2; C ? H···F and C ? H···N interactions for 3). Compound 1 shows solvent-dependent fluorescent properties with blue to green emission on the increasing of the solvent polarity. Compounds 2, 3 show blue photoluminescence in different solvents.     

Synthesis of Ph2LSn(μ-OH)Bu3SnCl. Trapping of monomeric triorganotin hydroxide Ph2LSnOH

The reaction of triorganotin(IV) compound Ph₂LSnCl (1), (L = 2,6-(t-BuOCH₂)₂C₆H₃), with (Bu₃Sn)₂O resulted to the isolation of Ph₂LSn(μ-OH)Bu₃SnCl (2), in which a monomeric triorganotin(IV) hydroxide Ph₂LSnOH intermolecularly coordinates Bu₃SnCl moiety. Compound 2 was characterized by combination of ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy, ESI/MS, elemental analysis and X-ray diffraction.     

Coordination chemistry of [Cp*Fe(η5-P3C2tBu2)] (Cp* = η5-C5Me5) with copper(I) halides – Formation of oligomeric and polymeric compounds

The reaction of the 1,2,4-triphosphaferrocene [Cp*Fe(η⁵-P₃C₂tBu₂)] (1) with CuX (X = Cl, Br, I) in a 1:1 stoichiometric ratio leads to the formation of the oligomeric compounds [{Cu(μ-X)}₆(μ₆-X)Cu(MeCN)₃{μ,η²-(Cp*Fe(η⁵-P₃C₂tBu₂))}₂{μ₃,η³-(Cp*Fe(η⁵-P₃C₂tBu₂))}] (X = Cl (2), Br (3)) and [{Cu(μ-I)}₃{Cu(μ₃-I)}₃Cu(μ₆-I){μ,η²-(Cp*Fe(η⁵-P₃C₂tBu₂))}₃{η¹-(Cp*Fe(η⁵-P₃C₂tBu₂))}] (4) revealing Cu(I) halide cages surrounded by 1,2,4-triphosphaferrocene moieties. The reaction of [Cp*Fe(η⁵-P₃C₂tBu₂)] with CuI in a 1:4 stoichiometry leads to the formation of the two-dimensional polymer [{Cu(μ-I)}₄{Cu(μ₃-I)(MeCN)}₂{μ₃,η³-(Cp*Fe(P₃C₂tBu₂))}]_n (5). The oligomeric compounds show dynamic behavior in solution monitored by ³¹P NMR spectroscopy. All compounds are additionally characterized by single crystal X-ray diffraction.