The hapticity of cyclooctatetraene in its first row mononuclear transition metal carbonyl complexes: Several examples of octahapto coordination

The two cyclooctatetraene metal carbonyls that have been synthesized are the tetrahapto derivative (η⁴-C₈H₈)Fe(CO)₃ and the hexahapto derivative (η⁶-C₈H₈)Cr(CO)₃ using the reactions of cyclooctatetraene with Fe(CO)₅ and with fac-(CH₃CN)₃Cr(CO)₃, respectively. Related C₈H₈M(CO)_n (M = Ti, V, Cr, Mn, Fe, Co, Ni; n = 4, 3, 2, 1) species have now been investigated by density functional theory in order to explore the scope of cyclooctatetraene metal carbonyl chemistry. In this connection, the existence of octahapto (η⁸-C₈H₈)M(CO)_n species is predicted as long as the central metal M does not exceed the 18-electron configuration by receiving eight electrons from the η⁸-C₈H₈ ring. Thus the lowest energy structures (η⁸-C₈H₈)Ti(CO)_n (n = 3, 2, 1), (η⁸-C₈H₈)M(CO)_n (M = V, Cr; n = 2, 1), and (η⁸-C₈H₈)Mn(CO) all have octahapto η⁸-C₈H₈ rings. An exception is (η⁶-C₈H₈)Fe(CO), with a hexahapto η⁶-C₈H₈ ring and thus only a 16-electron configuration for the iron atom. Hexahapto (η⁶-C₈H₈)M(CO)_n structures are predicted for the known (η⁶-C₈H₈)Cr(CO)₃ as well as the unknown (η⁶-C₈H₈)Ti(CO)₄, (η⁶-C₈H₈)V(CO)₃, (η⁶-C₈H₈)Mn(CO)₂, and (η⁶-C₈H₈)Fe(CO)₂ with 18, 18, 17, 17, and 18 electron configurations, respectively, for the central metal atoms. There are two types of tetrahapto C₈H₈M(CO)_n complexes. In the 1,2,3,4-tetrahapto (η⁴-C₈H₈)M(CO)_n complexes two adjacent CC double bonds, forming a 1,3-diene unit similar to butadiene, are bonded to the metal atom. In the 1,2,5,6-tetrahapto (η^2,2-C₈H₈)M(CO)₃ derivatives two non-adjacent CC double bonds of the C₈H₈ ring are bonded to the metal atom. The known (η⁴-C₈H₈)Fe(CO)₃ is a 1,2,3,4-tetrahapto complex. The unknown isomeric 1,2,5,6-tetrahapto complex (η^2,2-C₈H₈)Fe(CO)₃ is predicted to lie ∼15 kcal/mol above (η⁴-C₈H₈)Fe(CO)₃. The related 1,2,5,6-tetrahapto complexes (η^2,2-C₈H₈)Cr(CO)₄, (η^2,2-C₈H₈)Mn(CO)₄, [(η^2,2-C₈H₈)Mn(CO)₃]⁻, (η^2,2-C₈H₈)Co(CO)₂, and (η^2,2-C₈H₈)Ni(CO)₂ are all predicted to be low-energy structures.     

Formal chromium–chromium triple bonds and bent rings in the binuclear cycloheptatrienylchromium carbonyls (C7H7)2Cr2(CO)n (n = 6, 5, 4, 3, 2, 1, 0): A density functional theory study

Binuclear cycloheptatrienylchromium carbonyls of the type (C₇H₇)₂Cr₂(CO)_n (n = 6, 5, 4, 3, 2, 1, 0) have been investigated by density functional theory. Energetically competitive structures with fully bonded heptahapto η⁷-C₇H₇ rings are not found for (C₇H₇)₂Cr₂(CO)_n structures having two or more carbonyl groups. This result stands in contrast to the related (C_nH_n)₂M₂(CO)_n (M = Mn, n = 6; M = Fe, n = 5; M = Co, n = 4) systems. Most of the predicted (C₇H₇)₂Cr₂(CO)_n structures have bent trihapto or pentahapto C₇H₇ rings and CrCr distances in the range 2.4–2.5 Å suggesting formal triple bonds. In some cases rearrangement of the heptagonal C₇H₇ ring to a tridentate cyclopropyldivinyl or tridentate bis(carbene)alkyl ligand is observed. In addition structures with CO insertion into the C₇H₇–Cr bond are predicted for (C₇H₇)₂Cr₂(CO)_n (n = 6, 4, 2). The global minima found for the (C₇H₇)₂Cr₂(CO)_n derivatives for n = 6, 5, and 4 are (η⁵-C₇H₇)(OC)₂CrCr(CO)₄(η¹-C₇H₇), (η³-C₇H₇)(OC)₂CrCr(CO)₃(η^2,1- C₇H₇), and (η⁵-C₇H₇)₂Cr₂(CO)₄, respectively. The global minima for (C₇H₇)₂Cr₂(CO)_n (n = 3, 2) have rearranged C₇H₇ groups. Singlet and triplet structures with heptahapto η⁷-C₇H₇ rings are found for the dimetallocenes (η⁷-C₇H₇)₂Cr₂(CO) and (η⁷-C₇H₇)₂Cr₂, with the singlet structures being of much lower energies in both cases.     

Chemistry of vinylidene complexes. XVIII. Synthesis and molecular structure of the novel trinuclear μ3-vinylidene complex CpReFePt(μ3-CCHPh)(CO)6(PPh3)

The interaction between Cp(CO)₂RePt(μ-CCHPh)(PPh₃)₂ (1) and Fe₂(CO)₉ afforded the new heterometallic μ₃-vinylidene cluster CpReFePt(μ₃-CCHPh)(CO)₆(PPh₃) (2). An X-ray diffraction study shows the complex 2 possesses a trimetallic Re-Fe-Pt chain core. The bond lengths are Re-Fe 2.8221(8), Fe-Pt 2.5813(8) Å; the Re?Pt distance is 3.3523(7) Å; the bond angle Re-Fe-Pt is 76.55(3)°. The μ₃-CCHPh ligand is η¹-bound to the Re and Pt atoms and η²-coordinated to the Fe atom. The CC bond length is 1.412(4) Å. The Pt atom is coordinated by the PPh₃ and CO groups. Complex 2 is characterized by the IR and ¹H, ¹³C and ³¹P NMR spectra.     

Säureinduzierte carbin-acylumwandlung

The reaction of dicarbonyl- and carbonyl(trimethylphosphine)(cyclopentadienyl)-carbyne complexes of molybdenum and tungsten η⁵-C₅H₅(CO)_2−n(PMe₃)_nMCR (n = 0, 1; M = Mo, W; R = CH₃, C₆H₅, C₆H₄CH₃, C₃H₅) with protic nucleophiles HX (X = Cl, CF₃COO, CCl₃COO) leads, through a combined protonation/carbon-carbon coupling reaction, to η²-acyl complexes η⁵-C₅H₅(CO)_1−nX₂(PMe₃)_n-M(η²-COCH₂R). The reaction conditions, the results of the spectroscopic measurements and the X-ray structure of η⁵-C₅H₅(CO)(Cl₂)W(η²-COCH₂CH₃) are reported.     

Alkynyl Ti-M complexes based on M(CO)4 and MO2 building blocks (M = Mo, W)

The synthesis and properties of heterobimetallic Ti-M complexes of type {[[Ti](μ-η¹:η²-CCSiMe₃)][M(μ-η¹:η²-CCSiMe₃)(CO)₄]} (M = Mo: 5, [Ti] = (η⁵-C₅H₅)₂Ti; 6, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti; M = W: 7, [Ti] = (η⁵-C₅H₅)₂Ti; 8, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti) and {[Ti](μ-η¹:η²-CCSiMe₃)₂}MO₂ (M = Mo: 13, [Ti] = (η⁵-C₅H₅)₂Ti; 14, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti). M = W: 15, [Ti] = (η⁵-C₅H₅)₂Ti; 16, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti) are reported. Compounds 5-8 were accessible by treatment of [Ti](CCSiMe₃)₂ (1, [Ti] = (η⁵-C₅H₅)₂Ti; 2, [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti) with [M(CO)₅(thf)] (3, M = Mo; 4, M = W) or [M(CO)₄(nbd)] (9, M = Mo; 10, M = W; nbd = bicyclo[2.2.1]hepta-2,5-diene), while 13-16 could be obtained either by the subsequent reaction of 1 and 2 with [M(CO)₃(MeCN)₃] (11, M = Mo; 12, M = W) and oxygen, or directly by oxidation of 5-8 with air. A mechanism for the formation of 5-8 is postulated based on the in-situ generation of [Ti](CCSiMe₃)((η²-CCSiMe₃)M(CO)₅), {[Ti](μ-η¹:η²-CCSiMe₃)₂}-M(CO)₄, and [Ti](μ-η¹:η²-CCSiMe₃)((μ-CCSiMe₃)M(CO)₄) as a result of the chelating effect exerted by the bis(alkynyl) titanocene fragment and the steric constraints imposed by the M(CO)₄ entity.The molecular structure of 5 in the solid state were determined by single crystal X-ray diffraction analysis. In doubly alkynyl-bridged 5 the alkynides are bridging the metals Ti and Mo as a σ-donor to one metal and as a π-donor to the other with the [Ti](CCSiMe₃)₂Mo core being planar.     

Complexation and C-H bond activation of 1,5-cyclooctadiene on triosmium carbonyl clusters

Reaction of Os₃(CO)₁₀(NCMe)₂ and 1,5-cyclooctadiene (C₈H₁₂) affords the diene complex Os₃(CO)₁₀(η⁴-C₈H₁₂) (1) with the two alkene moieties coordinated to an equatorial and an axial positions of one osmium atom. Thermolysis of 1 in refluxing n-hexane results in a vinylic C-H bond activation to form (μ-H)Os₃(CO)₉(μ,η⁴-C₈H₁₁) (2) in good isolated yield. The crystal structures of 1 and 2 have been established by an X-ray diffraction study.     

Variable hapticity of the cyclooctatetraene ring in sandwich compounds of the first row transition metals

Density functional theory methods (B3LYP and BP86) indicate that the preferred structures for such early transition metal derivatives are (η⁸-C₈H₈)M(η⁴-C₈H₈) (M = Ti, V, Cr) with one octahapto η⁸-C₈H₈ ring and one tetrahapto η⁴-C₈H₈ ring. In such structures only 12 of the 16 carbon atoms of the two C₈H₈ rings are bonded to the metal, leading to 16-, 17-, and 18-electron complexes, respectively, in accord with the experimentally known structures for the Ti and V derivatives. The preferred structures for the Mn and Fe derivatives are (η⁶-C₈H₈)M(η⁴-C₈H₈) (M = Mn, Fe) with one hexahapto and one tetrahapto C₈H₈ ring and thus having 17- and 18-electron configurations, respectively, in accord with experimental data on the iron complex. The lowest energy structure for the cobalt complex is (η⁴-C₈H₈)Co(η^2,2-C₈H₈) with two different types of tetrahapto C₈H₈ rings and a 17-electron metal configuration. The nickel complex (C₈H₈)₂Ni appears to prefer a structure with a 16-electron configuration and two trihapto C₈H₈ rings, similar to the known (η³-C₃H₅)₂Ni rather than a bis(tetrahapto) structure with the favored 18-electron configuration. These theoretical studies indicate that in (C₈H₈)₂M derivatives of the first row transition metals, the number of carbon atoms in the pair of C₈H₈ rings involved in the bonding to the central metal atom gives the metal atoms 16-, 17-, or 18-electron configurations.     

Aminorhenium carbon dioxide complexes: formal oxidation of a carbon monoxide ligand with peroxy-acids or bromine/hydroxide

The electron-rich aminorhenium complexes η⁵:η¹-C₅H₄CH₂CH₂NR(CH₃)Re(CO)₂ (3a-d; R=methyl, benzyl, n-butyl, n-butyl-OH) are easily oxidized with peroxy-acids to give the corresponding η²-CO₂ complexes η⁵: η¹- C₅H₄CH₂CH₂NR(CH₃)Re(CO)(η²-CO₂) (4a-d) in excellent yield. The resultant η²-CO₂ complex is predominantly the anti-isomer. The structures of η²-CO₂ complex η⁵:η¹-C₅H₄CH₂CH₂N(CH₃)(n- C₄H₈OH)Re(CO)(η²-CO₂) (4d-anti) and the corresponding CO complex 3d have been confirmed by X-ray crystallography. The η²-CO₂ complexes 4a-4d are stable at ambient temperature under air. In addition to peroxy-acid oxidation, bromination of the aminorhenium dicarbonyl complexes followed by base treatment also provided the corresponding η²-CO₂ complexes. The reaction mechanism for the formation of CO₂ complex from the corresponding dicarbonyl is discussed briefly.     

Novel heterotetrametallic compounds derived from 1-(ferrocenylethynyl)(η6-arene)tricarbonylchromium

The synthesis and characterization of two new heterotetrametallic complexes are described. Reaction of [Cr(CO)₃(η⁶-C₆H₅)CC-{(η⁵-C₅H₄)Fe(η⁵-C₅H₅)}](1) with Co₂(CO)₈ or Cp₂Mo₂(CO)₄ afford the heterotetrametallic complexes [Cr(CO)₃(η⁶-C₆H₅){Co₂(CO)₆-μ²-η²-CC–}(η⁵-C₅H₄)Fe(η⁵-C₅H₅)}](2), and [Cr(CO)₃(η⁶-C₆H₅){Mo₂Cp₂(CO)₄-μ²-η²-CC–}(η⁵-C₅H₄)Fe(η⁵-C₅H₅)](3) in 80% and 41% yield, respectively. All complexes have been characterized by elemental analysis, multinuclear (¹H, ¹³C) NMR, and by single-crystal X-ray diffraction studies for 1 and 3. Structural data reveal that the coordination of dimolybdenum moiety to the alkyne unit influence the orientation of the carbonyl groups coordinated to the chromium as well as the Cp rings bound to the iron metal centre.     

Synthesis and structural characterization of [(C5H4)SiMe2(N-t-Bu)]Ti[(o-C6H4)C(Ph)C(Ph)], generated via an alkyne-Ti benzyne coupling reaction

The thermolysis of [(C₅H₄)SiMe₂(N-t-Bu)]TiPh₂ in the presence of diphenylacetylene proceeds at 80 °C in cyclohexane solution with the sole formation of the titanacyclic complex [(C₅H₄)SiMe₂(N-t-Bu)]Ti[(o-C₆H₄)C(Ph)C(Ph)], which has been characterized by solution NMR measurements and X-ray crystallographic analysis. This reaction is accompanied by the elimination of benzene and presumably occurs via coupling of a titanium benzyne intermediate with diphenylacetylene. The two chemically inequivalent Ti-C bonds of 2.081(7) and 2.103(6) Å in [(C₅H₄)SiMe₂(N-t-Bu)]Ti[(o-C₆H₄)C(Ph)C(Ph)] reflect the increased electrophilicity of the d⁰ Ti(IV) center arising from the presence of the bifunctional ansa-cyclopentadienyldimethylsilylamido ligand.     

A study of β-hydride abstraction from alkanediyl homobimetallic complexes [{Cp(CO)2Fe}2{μ-(CnH2n)}] (n = 4-10, Cp = η-C5H5)

The alkyl-bridged iron(II) complexes [{Cp(CO)₂Fe}₂{μ-(C_nH_2n)}] (n = 6-10, Cp = η⁵-C₅H₅) undergo both single and double hydride abstraction when reacted with one equivalent of Ph₃CPF₆ to give both the monocationic complexes, [{Cp(CO)₂Fe}₂{μ-(C_nH_2n−1)}]PF₆, and the dicationic complexes, [{Cp(CO)₂Fe}₂{μ-(C_nH_2n−2)}](PF₆)₂. The ratios of monocationic to dicationic complexes decrease with the increase in the value of n. The complexes where n = 4 and 5 undergo only single hydride abstraction under similar conditions. When reacted with two equivalents of Ph₃CPF₆, the complexes where n = 6-10 undergo double hydride abstraction to give dicationic complexes only. In contrast, the complex where n = 5 gives equal amounts of the monocationic and the dicationic complexes, while the complex where n = 4 only gives the monocationic complex. ¹H and ¹³C NMR data show that in the monocationic complexes one metal is σ-bonded to the carbenium ion moiety while the other is bonded in a η²-fashion forming a chiral metallacylopropane type structure. In the dicationic complexes both metals are bonded in the η²-fashion. The monocationic complexes where n = 4-6, react with methanol to give η¹-alkenyl complexes[Cp(CO)₂Fe(CH₂)_nCHCH₂] (n = 2-4) as the major products and σ-bonded ether products [{Cp(CO)₂Fe}₂{μ-(CH₂)_nCH(OCH₃)CH₂}] as the minor products. The complex where n = 8 reacted with iso-propanol to give the η¹-alkenyl complex [Cp(CO)₂Fe(CH₂)₆CHCH₂]. The dicationic complexes where n = 5, 8 and 9 were reacted with NaI to give the respective α, ω-dienes and [Cp(CO)₂FeI].     

Interfragment transmission of electronic effects of π-acceptor ligands in heterometallic triad complexes with trans-[Ru(Py)4(CN)2] as a central unit

The complex trans-[RuPy₄(CN)₂] cleaves chloride bridges in the binuclear rhodium(i) and palladium(ii) complexes [Rh(CO)₂Cl]₂, [Rh(η⁴-C₈H₁₂)Cl]₂, [(η⁴-C₈H₁₂)Rh(μ-Cl)₂Rh(CO)₂], [Pd(η³-C₃H₅)Cl]₂, and [(η₃-C₃H₅)Pd(μ-Cl)₂Rh(CO)₂] to form heterometallic triad complexes [(CO)₂ClRh(NC)RuPy₄(CN)RhCl(CO)₂] (1), [(η⁴-C₈H₁₂)ClRh(NC)RuPy₄(CN)RhCl-(η⁴-C₈H₁₂)] (2), [(CO)₂ClRh(NC)RuPy₄(CN)RhCl(η⁴-C₈H₁₂)] (3), [(η³-C₃H₅)ClPd(NC)-Ru(Py)₄(CN)PdCl(η³-C₃H₅)] (4), and [(CO)₂ClRh(NC)Ru(Py)₄(CN)PdCl(η₃-C₃H₅)] (5), respectively. In solutions, complex 3 coexists with equilibrium amounts of compounds 1 and 2; complex 5 is in the equilibrium with compounds 4 and 1. In both cases, the ratio of concentrations is close to binomial. Complexes 2 and 5 treated with [Rh(CO)₂Cl]₂ are converted into 1 with the simultaneous formation of [Rh(η⁴-C₈H₁₂)Cl]₂ and [Pd(η³-C₃H₅)Cl]₂, respectively. The δ_H and δ_C values for the ligands η⁴-C₈H₁₂, η³-C₃H₅, and CO are sensitive to the nature of the remote triad unit. The ligand effects are shown to be transmitted along the chain L′-M′-(NC)-Ru-(CN)-M″-L″.     

Zur Kenntnis der Chemie der Metallcarbonyle und der Cyanokomplexe in flüssigem Ammoniak. XXXII. Über die Reaktionen von η5-C5H5Mo(CO)3CH3 und η5-C5H5Fe(CO)2CH3 mit flüssigem Ammoniak

The Chemistry of Metal Carbonyls and Cyano Complexes in Liquid Ammonia. XXXII. On the Reaction of η⁵-C₅H₅Mo(CO)₃CH₃ and η⁵-C₅H₅Fe(CO)₂CH₃ with Liquid Ammonia η⁵-C₅H₅Mo(CO)₃CH₃ reacts with liquid NH₃ to give η⁵-C₅H₅Mo(CO)₂(NH₃)H and acetamide: In contrast, η⁵-C₅H₅Fe(CO)₂CH₃ undergoes a carbonyl insertion to give the acetyl complex η⁵-C₅H₅Fe(CO)(NH₃)COCH₃: The NH₃ ligand in η⁵-C₅H₅Fe(CO)(NH₃)COCH₃ can be substituted by pyridine.     

Synthesis and characterization of the unusual cluster [Ni2(GaAr′)2(η:η-μ2-C2H4)]: Ready addition of ethylene to Ni(COD)(GaAr′)2 at 25 °C and 1 atmosphere

The nickel (0) compound Ni(COD)(GaAr′)₂ (Ar′ = C₆H₃-2,6-(C₆H₃-2,6-i-Pr₂)₂), 1, was synthesized by the reaction of Ni(COD)₂ (COD = 1,5-cyclooctadiene) with (GaAr′)₂. Compound 1 reacted with ethylene at 25 °C and at 1 atm pressure to give the bimetallic cluster [Ni₂(GaAr′)₂(η¹:η¹-μ₂-C₂H₄)], 2, through the incorporation of one molecule of ethylene and displacement of COD. The structure of 2 featured an unusual Ni₂Ga₂C₂ core bicyclic structure in which the C₂H₄ moiety bridges the Ga···Ga edge of a Ga₂Ni₂ tetrahedron. The galliums each carry an η¹-bonded Ar′ substituent which complexes the nickel atom by an η⁶-π interaction with one of its flanking Ar’ rings.     

From straight chain to macrocyclic complexes containing mixed sulfur/nitrogen donors and coordinated 1,3-diynes

The acid-mediated reaction of [{Co₂(CO)₆(μ-η²-HOCH₂CC-)}₂] (1) with the meta- and para-substituted aminothiophenols, 3-NH₂-C₆H₄SH and 4-NH₂-C₆H₄SH, affords the straight chain species, [{Co₂(CO)₆(μ-η²-(3-NH₂-C₆H₄S)CH₂CC-)}₂] (2) and [{Co₂(CO)₆(μ-η²-(4-NH₂-C₆H₄S)CH₂CC-)}₂] (3), respectively. The molecular structure of 3 reveals the presence of two isomeric forms differing in the relative disposition of the S-aryl groups. Conversely, reaction of 1 with the ortho-substituted aminothiophenol, 2-NH₂-C₆H₄SH, furnishes the 10-membered macrocyclic species [{Co₂(CO)₆}₂{cyclo-μ-η²:μ-η²-CH₂C₂C₂CH₂SC₆H₃-NH-2}] (4) along with the linear chain complex [{Co₂(CO)₆(μ-η²-(2-NH₂-C₆H₄S)CH₂CC-)}₂] (5). On the other hand, treatment of 1 with the ortho-substituted mercaptopyridine, 2-SH-C₅H₄N, in the presence of HBF₄ gives the salt [{Co₂(CO)₆(μ-η²-(2-S-C₅H₄NH)CH₂CC-)}₂](BF₄)₂ (6a) in good yield; work-up in the presence of base affords the neutral complex [{Co₂(CO)₆(μ-η²-(2-S-C₅H₄N)CH₂CC-)}₂] (6b). Single crystal X-ray diffraction studies have been reported on 3-5 and 6a.     

Synthesis and characterization of triosmium and triruthenium pyrene clusters

The reaction between 1-pyrenecarboxaldehyde (C₁₆H₉CHO) and the labile triosmium cluster [Os₃(CO)₁₀(CH₃CN)₂] gives rise to the formation of two new compounds by competitive oxidative addition between the aldehydic group and an arene C-H bond, to afford the acyl complex [Os₃(CO)₁₀(μ-H)(μ-COC₁₆H₉)] (1) and the compound [Os₃(CO)₁₀(μ-H) (C₁₆H₈CHO)] (2), respectively. Thermolysis of [Os₃(CO)₁₀(μ-H)(μ-C₁₆H₉CO)] (1) in n-octane affords two new complexes in good yields, [Os₃(CO)₉(μ-H)₂(μ-COC₁₆H₈)] (3) and the pyryne complex [Os₃(CO)₉(μ-H)₂(μ₃-η¹:η¹:η²-C₁₆H₈)] (4).In contrast, when 1-pyrenecarboxaldehyde reacts with [Ru₃(CO)₁₂] only one product is obtained, [Ru₃(CO)₉(μ-H)₂(μ₃-η¹:η¹:η²-C₁₆H₈)] (5), a nonacarbonyl cluster bearing a pyrene ligand. All compounds were characterized by analytical and spectroscopic data, and crystal structures for 1, 2, 4 and 5 were obtained.     

Die thermische reaktion von C5H5(CO)2FeNa mit benzimidchloriden C6H5(Cl)CNR

η⁵-C₅H₅(CO)₂FeNa reacts with the benzimide chlorides C₆H₅(Cl)CNR (R  CH(CH₃)₂, C₆H₅) in boiling THF to give the η¹-iminoacyl complexes η⁵-C₅H₅ (CO)₂Fe[η¹-C(C₆H₅)NR]. Alternatively, the new Fe complexes [η⁵-C₅H₅(CO)Fe$\text{C(C}{}_6\text{H}{}_5\text{)N(CH}{}_3\text{)C(C}{}_6\text{H}{}_5\text{)N}$CH₃PF₆ (IV) and [η⁵-C₅H₅(CO)₂FeC(C₆H₅)N(CH₃)C(C₆H₅)NCH₃]PF₆ (V) are formed under the same conditions, if R  CH₃. Hudrolysis of the CN single bond of the ligand in V, not stabilized by a chelate effects as in IV, results in the formation of [η⁵-C₅H₅(CO)₂FeC(C₆H₅)NHCH₃]PF₆ (VII). Reaction of η⁵-C₅H₅(CO)₂ with N-benyzylbenzimido chloride yields η⁵-C₅H₅(CO)₂FeCH₂C₆H₅ as the only isolated product.     

Synthesis of Mo(CO)2(η-PPh2(o-C6H4)C(O)H)2 and its reaction with C60

Reaction of Mo(CO)₃(NCMe)₃ and PPh₂(o-C₆H₄)C(O)H (abbreviated as PCHO) at room temperature affords Mo(CO)₂(η³-PCHO)₂ (1), while compound 1 and the phosphine-imine complex Mo(CO)₄(η²-PPh₂(o-C₆H₄)CHNMe) (2) are obtained by using Mo(CO)₃(η³-(MeNCH₂)₃) as the reactant. Thermal reaction of 1 with C₆₀ products Mo(CO)₂(η⁴-(PPh₂(o-C₆H₄)CH)₂)(η²-C₆₀) (3) in low yield, apparently through coupling of the formyl moieties. The structures of 1 and 3 have been determined by an X-ray diffraction study. The two aldehyde groups of 1 and C₆₀ ligand of 3 are coordinated to the molybdenum atom in a π-fashion.     

Synthesis,molecular structure and reactivity of new π-conjugated diyne with ferrocenyl and phenyl units

New π-conjugated butadiynyl ligand FcC(CH₃)₂Fc′–CC–CC–Ph (L₁) has been synthesized and its reaction with Co₂(CO)₈ has been studied. New clusters [FcC(CH₃)₂Fc′–CC–CC–Ph][Co₂(CO)₆]_n [(1): n = 1; (2): n = 2] and [Fc–CC–CC–Ph][Co₂(CO)₆]_n [(3): n =  1; (4): n = 2] were obtained by the reaction of ligands FcC(CH₃)₂Fc′–CC–CC–Ph (L₁) and Fc–CC–CC–Ph (L₂) with Co₂(CO)₈ respectively and the composition and structure of the clusters and ligands have been characterized by elemental analysis, FTIR, ¹H and ¹³C NMR and MS. The crystal structures of compounds L₁, L₂, 2 and 4 have been determined by X-ray single crystal analysis.     

Syntheses and crystal structures of binuclear ruthenium complexes bearing 1,8′-bis(diphenylphosphinomethyl)naphthalene

Treatment of [RuCl₂(η⁶-C₆H₆)]_x with bidentate phosphine ligand BDNA [1,8-bis(diphenylphosphinomethyl)naphthalene] in methanol at room temperature gave η⁶-benzene-ruthenium complexes Ru₂Cl₄(η⁶-C₆H₆)₂(μ-BDNA) (1). Complex 1 further reacted with AgBF₄ to form complex [Ru₂Cl₂(μ-Cl)(η⁶-C₆H₆)₂(μ-BDNA)](BF₄) (2). [RuCl₂(η⁶-C₆H₆)]_x reacted with BDNA in refluxing methanol and then the reaction solution was treated with AgBF₄ to generate complex [Ru₂Cl₂(η⁶-C₆H₆)₂(μ-BDNA)₂](BF₄)₂ (3). Their compositions and structures had been determined by elemental analyses, NMR spectra and single crystal X-ray diffractions. X-ray diffraction showed that complex 1 belonged to monoclinic crystal system, P2₁/c space group with Z = 4, a = 12.810 Å, b = 21.507 Å, c = 18.471 Å, β = 107.95°; complex 2 belonged monoclinic crystal system, P2₁/n space group with Z = 4, a = 14.498 Å, b = 15.644 Å, c = 20.788 Å, β = 103.404°, and complex 3 belonged to monoclinic crystal system, P2₁/n space group with Z = 2, a = 13.732 Å, b = 14.351 Å, c = 19.733 Å, β = 94.82°.