19-Electron arenecyclopentadienyl complexes of ruthenium

A series of are necyc lope ntadienyl complexes,i. e., [Ru(⁵-c₅R₅)(⁶- are ne)]⁺ (1, R= H, arene = C₆H₆; 2, R = Me, arme = C₆H₆; 3, R = H, arctic = C₆H₃Me₃; 4, R = Me, arene = C₆H₃Me₃; 5, R = H, arene = C₆Me₆; 6, R = Me, arene = C₆Me₆) was studied by cyclic voltammetry. These compounds are capable of both oxidation and reduction. The reduction potential values depend on the number of methyl groups in the complex. Reduction of benzene complexes I and 2 by sodium amalgam in THF leads to the formation of decomplexation products, the addition of hydrogen to benzene, and dimerization of the benzene ligands. Both chemical and electrochemical reductions of mesitylene complexes3 and4 result in dimeric products [(⁵-C₅R₅)Ru(-⁵;⁵-Me₃H₃C₆H₃Me₃)Ru(⁵-C₅R₅)] (14, R = H; 15, R = Me). The action of sodium amalgam on compound5 gives products of hydrogen addition to both hexamethylbenzene (17) and cyclopentadienyl (18) ligands along with the major product, the dimer [⁵-C₅H₅)Ru(-⁵; ⁵-Me₆C₆C₆Me₆)Ru(⁵-C₅H₅)] (16). In contrast to5, its permcthylated analog 6 is only capable of adding hydrogen to the hexamethylbenzene ligand.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1691–1697, July, 1996.     

Isocyanide complexes of rhodium,part 41,2). η5-pentamethylcyclopentadienyl-rhodium (III) compounds

Summary The complexes Rh(⁵-C₅Me₅)(CNR)Cl₂, [Rh(⁵ - C₅Me₅)(CNR)₂Cl][PF₆], (R = Me, Et, i-Pr, t-Bu, C₆H₁₁, , p-CIC6H4 and 1-naphthyl), and [Rh(⁵-C⁵Me⁵)(CNR)₃][PF₆] (R = Et, i-Pr and t-Bu)] have been prepared by treatment of [Rh(⁵-C₅Me₅)Cl₂]₂ with RNC in the presence of [PF₆]^– (as appropriate). These complexes do not react with alcohols or amines to yield carbenes, but withm-MeC₆H₄SNa and NaS₂CNR₂, the species Rh(⁵-C₅H₅)(CNEt)(SC₆M₄Me-m)₂ and [Rh(⁵-C₅Me₅)(CNR)(S₂CNR₂)][PF₆] (R = Me, R¹ = Me or Et; R =p-ClC₆H₄, R¹ = Me) are formed. Treatment of [Rh(⁵-C₅H₅)(CNR)₂Cl][PF₆] with NaBH₄ gave low yields of compounds tentatively formulated as [Rh(⁵-C₅Me₅)(CNR)₂(BH₄)][PF₆] (R = Me or Et).Reprints of this article are not available.     

The pKR+ values for coordinated propargyl cations [Cp2M2(CO)4(μ-η2,η3-HC≡CCR1R2)]+ (M = Mo,W)

The pK_R+ values for metal-stabilized carbocations [Cp₂M₂(CO)₄(-²,³-HCCCR¹R²)]⁺ (M = Mo, W) containing primary (R¹ = R² = H), secondary (R¹ = H, R² = Me), or tertiary (R¹ = R² = Me) coordinated propargyl cations were measured in 50% aqueous acetonitrile. Their stability increases from the tertiary to primary cation, and the stability of the tungsten-containing cations is higher than that of the corresponding molybdenum analogs.     

Study of Redox-induced Reactions of Vinylidene and bis-Vinylidene Complexes of Manganese

Oxidative dehydrodimerization of some phenylvinylidene complexes of manganese is studied by cyclic voltammetry. In the case of (⁵-C₅H₅)(CO)₂Mn=C=C(H)Ph, the process occurs as the homolysis of the C–H bond in the radical cation of {(⁵-C₅H₅)(CO)₂Mn=C=C(H)Ph}^+· and the dimerization of intermediate -phenylethinyl cation [(⁵-C₅H₅)(CO)₂Mn–CC–Ph]⁺ to a binuclear dication of bis-carbine type (⁵-C₅H₅)(CO)₂Mn⁺C– C(Ph)=C(Ph)–CMn⁺(CO)₂(⁵-C₅H₅). The reduction of the latter leads to binuclear bis-vinylidene complex (⁵-C₅H₅)(CO)₂Mn=C=C(Ph)–C(Ph)=C=Mn(CO)₂(⁵-C₅H₅). Oxidative dehydrodimerization of complexes (⁵-C₅R₅)(CO)(L)Mn=C=C(H)Ph (R = H, L = PPh₃; R = Me, L = CO) occurs through the immediate C–C coupling of radical cations {(⁵-C₅R₅)(CO)(L)Mn=C=C(H)Ph}^+· and yields binuclear dication bis-carbine complexes (⁵-C₅R₅)(CO)(L)Mn⁺C–C(H)(Ph)–C(H)(Ph)–CMn⁺(CO)(L)(⁵-C₅R₅), whose reduction leads to neutral compounds (⁵-C₅H₅)(CO)₂Mn=C=C(Ph)–C(Ph)=C=Mn(CO)(L)(⁵-C₅H₅). Complex (⁵-C₅H₅)(CO)₂Mn=C=C(Ph)–C(Ph)=C=Mn(CO)₂(⁵-C₅H₅) undergoes the oxidation-induced nucleophilic addition of water, forming cyclic bis-carbene product with a bridge heterocyclic ligand (-3,4-diphenyl-2,5-dihydro-2,5-diylidene)-bis-(⁵-cyclopentadienyldicarbonyl manganese).     

Organometallic complexes containing thiosemicarbazone and related ligands. Part II(1). η3-allyl dicarbonyl complexes of molybdenum(II) with attached thiosemicarbazone ligands

Summary The -allylmolybdenum(II) complexes [MoX(CO)₂-(NCMe)₂(³-C₃H₄R)] (X=Cl, Br and I; R=H and 2-Me) react either in dichloromethane or acetonitrile with thiosemicarbazones to give the new complexes [MoX-(CO)₂(RRCNNHCSNH₂)(³-C₃H₄R)] (R=H or Me; R'=Me, Et, Pr or Ph)via displacement of acetonitrile ligands.     

Hetero- and homobimetallic M/Ni,M/M (M = Mo,W) μ-alkyne complexes containing functionally substituted cyclopentadienyl ligands. Crystal structure of η5-2,4-(NO2)2C6H3NHNC(Me)C5H4(CO)2WFe2H(μ3-S)(CO)6

While reaction of [⁵-RC₅H₄(CO)₃Mo]₂, PhCCPh and Cp₂Ni yields Mo/Ni hetero- and Mo/Mo homobimetallic complexes [⁵-RC₅H₄(CO)₂MoNiCp](-C₂Ph₂) [(1a) R = MeCO; (1b) R = MeO₂C] and [⁵-RC₅H₄(CO)₂Mo]₂(-C₂Ph₂) [(2a) R = MeCO; (2b) R = MeO₂C], reaction of [⁵-RC₅H₄(CO)₃W]₂, PhCCPh and Cp₂Ni give W/Ni heterobimetallic compounds [⁵-RC₅H₄(CO)₂WNiCp](-C₂Ph₂) [(3a) R = MeCO; (3b) R = EtO₂C] without an appreciable amount of W/W homobimetallic complexes [⁵-RC₅H₄(CO)₂W]₂(-C₂Ph₂) [(4a) R = MeCO; (4b) R = EtO₂C]. However, (4a) and (4b) can be simply obtained from [⁵-RC₅H₄(CO)₃W]₂ and PhCCPh in quite good yields. Further, reactions of (1a) and (3a) with 2,4-(NO₂)₂C₆H₃NHNH₂ produce phenylhydrazone derivatives [⁵-2,4-(NO₂)₂C₆H₃NHNC(Me)C₅H₄(CO)₂MNiCp](-C₂Ph₂) [(5a) M = Mo, (5b) M = W], whereas reactions of (2a) and (4a) with 2,4-(NO₂)₂C₆H₃NHNH₂ give corresponding derivatives [⁵-2,4-(NO₂)₂C₆H₃NHNC(Me)C₅H₄(CO)₂MM(CO)₂C₅H₄COMe-⁵](-C₂Ph₂) [(6a) M = Mo, (6b) M = W] and [⁵-2, 4-(NO₂)₂C₆H₃NHNC(Me)C₅H₄(CO)₂M]₂(-C₂ Ph₂) [(7a) M = Mo, (7b) M = W]. The crystal structure of ⁵-2,4-(NO₂)₂C₆H₃NHNC(Me)C₅H₄(CO)₂WFe₂H (₃-S)(CO)₆ (8) has been determined by X-ray diffraction.     

Isostructural triazenido complexes of first row transition metals. Part 2. Synthesis and properties of [(η5-C5H5)L(RN3R)CoIII]PF6, L = PEt3, PPh3, P(OMe)3 and P(OPh)3

Summary The synthesis and properties of the [(⁵-C₅H₅)L(RN₃R)Co^III]PF₆ complexes, with L = PEt₃, PPh₃, P(OMe)₃ or P(OPh)₃, are reported. A six coordinate configuration containing a chelating triazenido ligand is proposed which is isostructural with the known complexes of iron and nickel.The spectroscopic properties of the isoelectronic Co and Fe complexes, (⁵-C₅H₅)L(RN₃R)M, are compared in relation to the charge on the central metal atom. The complex with L = CO could not be prepared, but the carbonyl inserted product (⁵-C₅H₅)(L{RNNN(R)C(O)}Co was isolated. In one of the reactions, the novel ring-bound triphenylphosphine complex, [⁵-C₅H₅)(⁵-C₅H₄PPh₃)Co^III](PF₆)₂, was isolated as a side product. The mechanism of this reaction is discussed.     

Germylenes and stannylenes based on aminobisphenolate ligands: insertion into the C—Br bond

A reaction of previously synthesized germylenes and stannylenes based on aminobisphenols RN{CH₂[(5-R´)(3-But)C₆H₂(2-O—)]}₂M^II, M = Ge, R = CH²(2-Py), R´ = But (1); M = Ge, R = Et, R´ = Me (2); M = Sn, R = CH₂(2-Py), R´ = But (3); M = Sn, R = Et, R´ = Me (4), containing (tetrylenes 1 and 3) or not containing (tetrylenes 2 and 4) a group capable of additional donation, with allyl bromide leads to the products of the insertion of tetrylenes into the C—Br bond: RN{CH₂[(5-R´)(3-Bu^t)C₆H₂(2-O—)]}₂M(Br)All, M = Ge, R = CH₂(2-Py), R´ = But (5); M = Ge, R = Et, R´ = Me (6); M = Sn, R = CH₂(2-Py), R´ = But (7); M = Sn, R = Et, R´ = Me (8). The structures of obtained derivatives were confirmed by NMR spectroscopy and elemental analysis. The structures of compounds 4, 5, and 7 were studied by X-ray crystallography. Stannylene 4 was found to be monomeric in the solid phase: the coordination number of the Sn atom is 3. The insertion products 5 and 7 are characterized by the coordination number 6 for the central atom.     

Synthesis and investigation of mono- and binuclear cyano-bridged complexes of rhodium,ruthenium, and palladium

Binuclear Rh^III and Ru^II complexes of the [M¹-CN-M²]⁺BF ₄ ^– (M¹ and/or M² are (⁵-Cp)(³-C₃H₅)Rh and (⁶-C₆H₆)(³-C₃H₅)Ru) type, heteronuclear organometallic compound (⁵-Cp)(³-C₃H₅)RhCNPd(³-C₃H₅)Cl, and mononuclear Rh^III and Ru^II complexes [(³-C₃H₅)LM(MeCN)]⁺ _BF4 ^– (M = Rh, L = ⁵-Cp; M = Ru, L = ⁶-C₆H₆) were synthesized. An electrochemical study of these compounds in solutions demonstrates that the bond between the bridged CN ligand and the metal atoms is rather strong, and there is no dissociation into mononuclear fragments in solutions. The kinetics of the reaction of [(⁵-Cp)(³-C₃H₅)Rh(MeCN)]⁺ _BF4 ^– with halide ions was studied by electrochemical methods. The ligand exchange proceeds by a bimolecular dissociative-exchange mechanism.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 968–973, May, 1995.     

The chemistry of cyclopentadienyl nitrosyl and related complexes of molybdenum,part 10(1). Cationic allyl complexes and attack thereon by nucleophiles

Summary The syntheses of [Mo(⁵-C₅H₅)(³-C₃H₄R)(CO)(NO)]⁺ (R=H, 1- or 2-Me) and [Mo(⁵-C₅H₅)(³-C₃H₅)(NCR)(NO)]⁺ (R=Me or Ph), by treatment of Mo(⁵-C₅H₅)(CO)₂(NO) with RC₃H₄Br and Ag⁺, and of Mo(⁵-C₅H₅)(³-C₃H₅)(NO)I with Ag⁺ in the presence of RCN, is described. Treatment of these cations with nucleophiles gives Mo(⁵-C₅H₅)(³-C₃H₅)(NO)X (X=halide, NCS or NCO), Mo(⁵-C₅H₅)(³-C₃H₅Q)(CO)(NO) (C₃H₅Q= propene ligand, Q= H, SCOMe, SEt, S₂CNMe₂, S₂CNEt₂, S₂CN(Bu-n)₂, C₅H₅, acac, OH, OMe or OAc), and [Mo(⁵-C₅H₅)(₂C₃H₅L)(CO)(NO)]⁺ (L=PEt₃, n-Bu₃P, PPh₃, PPh₂H, PMe₂Ph, C₅H₅N, 1-, 3- or 4-MeC₅H₄N and Me₂NNH₂). Reaction of [Mo(⁵-C₅H₅)(³-C₃H₅)(NCMe)(NO)⁺ with pyridine gave [Mo(⁵-C₅H₅)(³-C₃H₅)(pyr)(NO)]⁺, while treatment of [Mo(⁵-C₅H₅)(³-C₃H₅)(CO)(NO)]⁺ with PPh₃ in the presence of NaOEt afforded Mo(⁵-C₅H₅)(CO)(NO)(PPh₃). The¹H and¹³C n.m.r. spectra of these complexes are discussed particularly in relation to the occurrence ofexo andendo isomers of the allylic species. Comparison is made briefly between Mo(⁵-C₅H₅)(³-C₃H₅)(NO)I and Mo(C₅H₅)₂(NO)I.     

Tetrahedral and heteronuclear transition metal clusters through isolobal displacements and functional transformations

The isolobal reaction of the tetrahedral cluster Ph₂C₂Co₂(CO)₆with ⁵-CHOC₅H₄(CO)₃MNa (M = Mo, W) yields ⁵-CHOC₅H₄MCoC₂Ph₂(CO)₅ [(1) M = Mo, (2) M = W], whereas M–M singly-bonded dimers [⁵-RC₅H₄- M(CO)₃]₂ [M = Mo, R = Ac; M = Mo, W, R = CHO] react with Co₂(CO)₈ to give ⁵-AcC₅H₄MoCo₃(CO)₁₁ (7) and ⁵-C₅H₅MCo₃(CO)₁₁ [(8) M = Mo, (9) M = W], respectively. While (1) and (2) react with 2,4-dinitrophenylhydrazine to give phenylhydrazone derivatives ⁵-2,4-(NO₂)₂C₆H₃NHN=CHC₅H₄MCoC₂Ph₂(CO)₅ [(3) M = Mo, (4) M = W], treatment of ⁵-AcC₅H₄MCoFe(CO)₈(₃-S) with 2,4-dinitrophenylhydrazine produces corresponding derivatives ⁵-2,4-(NO₂)₂C₆H₃NHN=C(Me)C₅H₄MCoFe(CO)₈(₃-S) [(5) M = Mo, (6) M = W]. In addition, the cyclopentadienylformaldehyde ligand in the ⁵-CHOC₅H₄MoCoFe(CO)₈(₃-S) cluster can be decarbonylated in the presence of Co₂(CO)₈ to give the parent cluster ⁵-C₅H₅MoCoFe(CO)₈(₃-S)(10). This observation, together with the formation of (8) and (9) in the presence of Co₂(CO)₈ can be explained by the proposed mechanism.     

Acyl iodides in organic synthesis: VII. Reactions with trialkyl(alkynyl)silanes,-germanes, and-stannanes

Reactions of acyl iodides R¹COI (R¹=Me, Ph) with trialkyl(alkynyl)silanes,-germanes, and stannanes (R²C≡CMR ₃ ³ ; M=Si, Ge, Sn) were studied. Acyl iodides reacted with the germanium and tin derivatives with cleavage of the M-C_sp bond and formation of the corresponding trialkyl(iodo)germanes and-stannanes R ₃ ³ MI (M=Ge, Sn) and alkynyl ketones R¹C(O)C≡CR² and R¹C(O)C≡CC(O)R¹. By contrast, the reaction of acetyl iodide with ethynyl(trimethyl)silane gave only a small amount of 1,2-diiodovinyl(trimethyl) silance as a result of iodine addition at the triple bond. Bis(trimethylsilyl)ethyne failed to react with acetyl iodide.     

Reactions of diphenylphosphine and methyldiphenylphosphine with (η3-allyl)dicarbonylchlorobis(methyl cyanide)molybdenum and-tungsten: Mechanistic implications in the reductive elimination of allyl halides

Summary Reactions of L = PHPh₂ or PMePh₂ with [MCl(CO)₂(³-C₃H₄R)(MeCN)₂] (M = Mo, R = H or Me; M = W, R = H) in MeOH involve initial substitution to give [MCl(CO)₂(³-C₃H₄R)L₂]. In MeCN, an excess of tertiary phosphine readily causes reductive elimination of allyl halide with the formation ofmer-[M(CO)₂(MeCN)L₃]. The molybdenum analogue can also be produced in high yields by reacting PMePh₂ with either [Mo(CO)₂(³-C₃H₅)(MeCN)₃]BF₄ or Ph₄As[Mo₂Cl₃(CO)₄(³-C₃H₅)₂]. During these reactions, the new [MCl₂(CO)₂(³-C₃H₅)(PMePh₂)]^– anions were formed and isolated as their -allylphosphonium salts. Under forcing conditions, reactions involving PHPh₂ also resulted in elimination of the allyl group giving high yields ofcis-M(CO)₂(PHPh₂)₄. The relevance of these observations on the mechanism of the reduction process are discussed.     

Darstellung,Charakterisierung und Struktur funktionalisierter Fluorphosphaalkene des Typs R3E–P=C(F)NEt2 (R/E = Me/Si,Me/Ge,CF3/Ge,Me/Sn)

Preparation, Characterization, and Structure of Functionalized Fluorophosphaalkenes of the Type R₃E–P=C(F)NEt₂ (R/E = Me/Si, Me/Ge, CF₃/Ge, Me/Sn) P‐functionalized 1‐diethylamino‐1‐fluoro‐2‐phosphaalkenes of the type R₃E–P=C(F)NEt₂ [R/E = Me/Si ( 2 ), Me/Ge ( 3 ), CF₃/Ge ( 4 ), Me/Sn ( 5 )] are prepared by reaction of HP=C(F)NEt₂ ( 1 , E/Z = 18/82) with R₃EX (X = I, Cl) in the presence of triethylamine as base, exclusively as Z‐Isomers. 2–5 are thermolabile, so that only the more stable representatives 2 and 4 can be isolated in pure form and fully characterized. 3 and 5 decompose already at temperatures above –10 °C, but are clearly identified by ¹⁹F and ³¹P NMR‐measurements. The Z configuration is established on the basis of typical NMR data, an X‐ray diffraction analysis of 4 and ab initio calculations for E and Z configurations of the model compound Me₃Si–P=C(F)NMe₂. The relatively stable derivative 2 is used as an educt for reactions with pivaloyl‐, adamantoyl‐, and benzoylchloride, respectively, which by cleavage of the Si–P bond yield the push/pull phosphaalkenes RC(O)–P=C(F)NEt₂ [R = tBu ( 6 ), Ad ( 7 ), Ph ( 8 )], in which π‐delocalization with the P=C double bond occurs both with the lone pair on nitrogen and with the carbonyl group.     

Oxidation of isomeric η6- and η5-fluorenylchromiumtricarbonyl anions

The oxidation of the carbon-centered [(⁶-C₁₃H₉)Cr(CO)₃]^– anion (1 ^–) results in formation of (-⁶:⁶-9,9-bifluorenyl)bis-chromiumtricarbonyl (3) due to coupling of the intermediate carbon-centered radical (1^.). The oxidation of the metal-centered anion [(⁵-C₁₃H₉)Cr(CO)₃]^– (2 ^–), which is isomeric to the 1^– anion, gives an equilibrium mixture of the chromium-centered radical {(⁵-C₁₃H₉)Cr(CO)₃}^. (2 ^.) and its dimer [(⁵-C₁₃H₉)Cr(CO)₃]₂ (6). Radical2 ^. readily reacts with MeI and the solvent (THF); the resulting derivatives, (⁵-C₁₃H₉)Cr(CO)₃R (R=Me (10); R=H (7)), undergo fast ricochet inter-ring ⁵⁶ rearrangements into (⁶-9R-C₁₃H₉)Cr(CO)₃ (R=CH₃ (9); R=H (4)).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1354–1358, July, 1995.The authors are grateful to D. V. Zagorevskii who recorded the mass spectra. This study was financially supported by the Russian Foundation for Basic Research (Grant No. 94-03-05209) and the International Science Foundation (Grant Nos. MQ 4000 and REV 000).     

Formation of closo-rhodacarboranes containing η2,η3-(CH2=CHC5H6) ligand in the reaction of μ-dichloro-bis[(η4-norbornadiene)rhodium] with nido-dicarbaundecaborates [K][nido-7-R1-8-R2-7,8-C2B9H10]

The reactions of a complex [(⁴-C₇H₈)RhCl]₂ (C₇H₈ is norbornadiene) with salts of substituted nido-dicarbaundecaborates, [K][nido-7-R¹-8-R²-7,8-C₂B₉H₁₀] (R¹ = R² = H (a); R¹ = R² = Me (b); R¹, R² = 1,2-(CH₂)₂C₆H₄ (c); R¹ = Me, R² = Ph (d)), in CH₂Cl₂ afforded new closo-(²,³-(4-vinylcyclopenten-3-yl))rhodacarboranes. The structures of the compounds were studied by multinuclear NMR spectroscopy. A probable mechanism of the rearrangement of the norbornadiene ligand is discussed.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1875–1878, September, 2004.     

On the possibility of existence of η5-π-complexes of C60 fullerene: π-complexes with silicon

Qualitative estimates of possibility of the formation of fullerene ⁵--complexes have been carried out by the MNDO/PM3 method. It was shown, as exemplified by the C₆₀ cluster, that the introduction of five univalent functional groups R (R = H, Cl, Br) to -positions of a separate pentagon of C₆₀ with the formation of [R₅C₆₀]^– anions results in a pronounced increase in the -electron density on the atoms of this five-membered cycle and more favorable conditions for the formation of -bonds with the ⁵-ligand. The nature of the interaction between the atoms of the separate cycle in [R₅C₆₀]^– anion and ⁵-ligand was analyzed by the example of hypothetical sandwich systems R₅C₆₀SiCp. Half-sandwich complexes R₅C₆₀SiX (X = H, Cl) were also investigated. The local energy minima were found on the potential energy surfaces (PES) of systems R₅C₆₀SiCp and R₅C₆₀SiX with C_5p symmetry. These systems transform barrirlessly into q5-7E-complexes with the angular structure if the symmetry restrictions are removed. The most favorable conditions for ⁵--complexes of R₅C₆₀ to form are realized for R = H. The results obtained were compared to those of semiempirical and nonempirical calculations of bis (cyclopentadienyl) silicon.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2422–2429, October, 1996.     

Preparation and properties of palladium(II) and rhodium(I) complexes containing bidentate phosphine sulphide and selenide ligands

Summary The synthesis and properties of cationic complexes of general formula [ML₂{CH₂(Ph₂PE)₂}]BF₄, where M = Pd^II and Rh^II, L₂ = ³-MeC₃H₄, {P(O)(OR)₂}₂H (R = Me, Et), COD, (CO)₂, (CO)PPh₃ and E = S, Se are described. The methylene proton of the coordinated phosphine sulphide or selenide ligands react with strong bases as BuLi in n-hexane or NaH in THF, to give neutral complexes of the type [ML₂{CH(Ph₂PE)₂}], where M = Pd^II, Rh^I; L₂ = ³-MeC₃H₄, COD and E = S, Se. The complexes have been characterized by elemental analyses, molar conductivities, i.r., ¹H n.m.r. and ³¹P{¹H} n.m.r. spectroscopy.     

η-Cyclopentadienyl(nitrosyl)iron complexes containing group VA donors

Summary [(-C₅H₅)Fe(NO)(CO)]₂ and (-C₅H₅)Fe(NO)(CO)I are formed when a slow stream of NO is passed through a benzene solution of [(-C₅H₅)Fe(CO)₂]₂ and (-C₅H₅)Fe(CO)₂ I respectively. Similarly NO reacts with (-C₅H₅)Fe(CO)(Ph₃E)I and [(-C₅H₅)Fe(CO)₂(Ph₃E)]I, where E = P, As and Sb, to give (-C₅H₅)Fe(NO)(Ph₃E)I and [(-C₅H₅)Fe(NO)₂(Ph₃E)]I respectively. The complexes were characterized by elemental analyses and i.r. spectra.Reprints of this article are not available.     

Mixed-Metal Cluster Chemistry. 27. Coupling of Diphenylbuta-1,3-diyne and CO at Tungsten–Triiridium Cluster Cores

Reactions of WIr₃(CO)₁₁(-C₅H₄R) (R=H, Me) and excess diphenylbuta-1,3-diyne in refluxing toluene afford a large number of products in each case, one of which has been identified as [WIr₃{ ₄- ⁷-C(Ph)C(C CPh)C(Ph)CC(H)CC₆H₄ C(O)-2}(CO)₇(-C₅H₄R)] [R=H (10 %) (1), Me (6 %)] by a single-crystal X-ray diffraction study of 1. The structure of 1 reveals a unique ten-electron-donating ligand which has formed from combination of two diphenylbuta-1,3-diyne units and one carbonyl group, addition of the latter having presumably proceeded by orthometallation of one phenyl group, followed by formal insertion of the carbonyl into the Ir-phenyl linkage. Crystal data for 1.CH₂Cl₂: space group P2₁/n, a = 8.6081(1)Å, b = 39.3638(5)Å, c = 12.3935(2)Å, = 100.4889(5)°, V = 4129.33(10)ų, Z = 4, R = 0.030, R _w = 0.026 for 4982 reflections [I > 2.00(I)]