Synthesis,Characterization and Reactivity of the Tricarbonyl(formylcycloheptatrienyl)iron‐Anion [(η3‐C7H6CHO)Fe(CO)3]−

Deprotonation of the readily available organometallic aldehyde derivative [(η⁴‐C₇H₇CHO)Fe(CO)₃] ( 2 ) with NaN(SiMe₃)₂ in benzene solution at ambient temperature afforded the anionic formylcycloheptatrienyl complex Na[(η³‐C₇H₆CHO)Fe(CO)₃] ( 3 ). The anion is fluxional in solution and displays a unique ambident reactivity towards electrophiles (MeI, Me₃SiCl). New substituted [(η⁴‐RC₇H₆CHO)Fe(CO)₃] and [(η⁴‐heptafulvene)Fe(CO)₃] complexes have been identified as the products. Treatment of 3 with 0.5 equivalents of dimeric [(COD)RhCl]₂ (COD = 1,5‐cyclooctadiene) afforded the functionalized Fe‐Rh cycloheptatrienyl complex [(μ‐C₇H₆CHO)(CO)₃FeRh(COD)] ( 7 ) in up to 86 % yield. Carbonylation of 7 under an atmosphere of CO led to facile conversion to the heterobimetallic pentacarbonyl derivative [(μ‐C₇H₆CHO)(CO)₃FeRh(CO)₂] ( 8 ), which is also accessible in lower yield from the direct reaction of 3 with [Rh(CO)₂Cl]₂.     

Kinetics of nucleophilic attack on coordinated organic moieties : VI. Mechanism of addition of tri-n-butylphosphine to [(C7H7)M(CO)3]BF4 (M = Cr, Mo, W) and related cations

Phosphonium adduct formation via attack of tri-n-butylphosphine on the cations [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo, W) obeys the rate law, Rate = k [complex] [PBu₃]. The very similar rate constants for the Cr, Mo and W complexes confirm the similar electrophilicities of the tropylium rings in these cations, and also support the view that there is direct addition to the rings. The related complexes [(C₆H₇)Fe(CO)₃]BF₄ and [(C₆H₆)Mn(CO)₃]BF₄ also form adducts with PBu₃, and the quantitative reactivity order [(C₆H₇)Fe(CO)₃]⁺ > [(C₇H₇)Cr(CO)₃]⁺ » [(C₆H₆)Mn(CO)₃]⁺ (160:60:1) has been established.     

Heterobimetallische phosphanido-verbrückte Zweikern-Komplexe - Synthese von cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6−iPr3C6H2)}2M(CO)4] (RMe,MCr,Mo; RH,MMo)

Heterobimetallic Phosphanido-bridged Dinuclear Complexes - Syntheses of cis-rac-[(η-C₅H₄R)₂Zr{μ-PH(2,4,6-ⁱPr₃C₆H₂)}₂M(CO)₄] (R?Me, M?Cr, Mo; R?H, M?Mo) The zirconocene bisphosphanido complexes [(η-C₅H₄R)₂Zr{PH(2,4,6-ⁱPr₃C₆H₂)}₂] (R?Me, H) react with [(NBD)M(CO)₄] (NBD?norbornadiene, M?Cr, Mo) to give only one diastereomer of the phosphanido-bridged heterobimetallic dinuclear complexes cis-rac-[(η-C₅H₄R)₂Zr{μ-PH(2,4,6-ⁱPr₃C₆H₂)}₂M(CO)₄] [R?Me, M?Cr ( 1 ), Mo ( 2 ); R?H, M?Mo ( 3 )]. However, no reaction was observed between [(η-C₅H₅)₂Zr{PH(2,4,6-^tBu₃ C₆H₂)}₂] and [Pt(PPh₃)₄]. 1—3 were characterised spectroscopically. For 1—3 , the presence of the racemic isomer was shown by NMR spectroscopy. No reaction was observed at room temperature for 3 and CS₂, (NO)BF₄, Me₃NO or PH(2,4,6-Me₃C₆H₂)₂. With Et₂AlH or PhC?CH decomposition of 3 was observed.     

[(C2H5)3NH]2Sn3Se7 · 0,25 H2O und [(C3H7)2NH2]4Sn4Se10 · 4 H2O

Synthesis, Structure, and Properties of Some Selenidostannates. II. [(C₂H₅)₃NH]₂Sn₃Se₇ · 0,25 H₂O and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O The new selenidostannate hydrates [(C₂H₅)₃NH]₂Sn₃Se₇ · 0.25 H₂O ( I ) and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O ( II ) were synthesized from an aqueous suspension of triethylammonium (tripropylammonium), tin, selenium I and in addition sulfur II at 130 °C. I crystallizes at ambient temperature in the monoclinic space group P2₁/n (a = 2069,3(4) pm, b = 1396,6(3) pm, c = 2342,8(5) pm, β = 114,68(3)°, Z = 8) and is characterized by two different anions, chains from edge‐sharing [Se₃Se₇]^2– units and nets from trigonal SnSe₅ bipyramids. II crystallizes at ambient temperature in the tetragonal space group I4₁/amd (a = 2150,0(3) pm, c = 1174,4(2) pm, Z = 4) and contains adamantane like [Sn₄Se₁₀]^4–‐cages. The UV‐VIS spectra of the selenidostannates demonstrate that the absorption edges red shift as the dimensionality of the compounds is increased.     

Reaktionen der Cycloheptatrienylkomplexe [η7-C7H7W(CO)3]BF4 und η7-C7H7Mo(CO)2 Br mit Neutralliganden und die elektrochemische Reduktion des Wolframkomplexes

Reactions of the Cycloheptatrienyl Complexes [η⁷-C₇H₇W(CO)₃]BF₄ and η⁷-C₇H₇Mo(CO)₂Br with Neutral Ligands and the Electrochemical Reduction of the Wolfram Complex Compounds of the type [η⁷-C₇H₇M(CO)₂L][BF₄] (L = P(C₆H₅)₃, As(C₆H₅)₃, Sb(C₆H₅)₃ for M = W and L = N₂H₄ for M = Mo) were synthesized and characterisized. The iodide η⁷-C₇H₇W(CO)₂I reacts with the diphosphine ((C₆H₅)₂PCH₂)₂ to give the trihapto complex η³-C₇H₇ W(CO)₂I((C₆H₅)₂PCH₂)₂. In the case of η⁷-C₇H₇Mo(CO)₂ Br reaction with hydrazine leads to the substitution product [η⁷-C₇H₇ Mo(CO)₂N₂H₄]^⊕, which can be stabilized by large anions. The binuclear complex [C₇H₇W(CO)₃]₂ has been synthesized electrochemically.     

Synthese und Kristallstruktur von (C5H5)Mo(CO)3(AuPPh3) und [(C5H5)Mo(CO)2(AuPPh3)4]PF6

Synthesis and Crystal Structure of (C₅H₅)Mo(CO)₃(AuPPh₃) and [(C₅H₅)Mo(CO)₂(AuPPh₃)₄]PF₆ CpMo(CO)₃(AuPPh₃) is obtained by the reaction of Li[CpMo(CO)₃] with Ph₃PAuCl at ?95°C in CH₂Cl₂. It crystallizes in the monoclinic space group C2/c with a = 2625.1(7), b = 883.2(1), c = 2328.4(7) pm, β = 116.39(1)° und Z = 8. In the complex the AuPPh₃ group is coordinated to the CpMo(CO)₃ fragment with a Au? Mo bond of 271,0 pm. The Mo atom thus achieves a square pyramidal coordination with the center of the Cp ring in apical position. CpMo(CO)₃(AuPPh₃) reacts under uv irradiation with an excess of Ph₃PAuN₃ to afford the cluster cation [CpMo(CO)₂(AuPPh₃)₄]⁺. It crystallizes as [CpMo(CO)₂(AuPPh₃)₄]PF₆ · 2 CH₂Cl₂ in the orthorhombic space group P2₁2₁2₁ with a = 1553.9(1), b = 1793.8(2), c = 2809.8(7) pm und Z = 4. The five metal atoms form a trigonal bipyramidal cluster skeleton with the Mo atom in equatorial position. The Mo? Au distances range from 275.5 to 280.8 pm, and the Au? Au distances are between 281.2 and 285.6 pm.     

Synthese,Struktur und Reaktivität des Ferrioarsaalkens [(η5‐C5Me5)(CO)2FeAs=C(Ph)NMe2]

Synthesis, Structure, and Reactivity of the Ferrioarsaalkene [(η⁵‐C₅Me₅)(CO)₂FeAs=C(Ph)NMe₂] Reaction of equimolar amounts of the carbenium iodide [Me₂N(Ph)CSMe]I and LiAs(SiMe₃)₂ · 1.5 THF afforded the thermolabile arsaalkene Me₃SiAs = C(Ph)NMe₂ ( 1 ), which in situ was converted into the black crystalline ferrioarsaalkene [(η⁵‐C₅Me₅)(CO)₂FeAs=C(Ph)NMe₂)] ( 2 ) by treatment with [(η⁵‐C₅Me₅)(CO)₂FeCl]. Compound 2 was protonated by ethereal HBF₄ to yield [(η⁵‐C₅Me₅)(CO)₂FeAs(H)C(Ph)NMe₂]BF₄ ( 3 ) and methylated by CF₃SO₃Me to give [(η⁵‐C₅Me₅)(CO)₂FeAs(Me)C(Ph)NMe₂]‐ SO₃CF₃ ( 4 ). [(η⁵‐C₅Me₅)(CO)₂FeAs[M(CO)_n]C(Ph)NMe₂] ( 5 : [M(CO)_n] = [Fe(CO)₄]; 6 : [Cr(CO)₅]) were isolated from the reaction of 2 with [Fe₂(CO)₉] or [{(Z)‐cyclooctene}Cr(CO)₅], respectively. Compounds 2 – 6 were characterized by means of elemental analyses and spectroscopy (IR, ¹H, ¹³C{¹H}‐NMR). The molecular structure of 2 was determined by X‐ray diffraction analysis.     

Charakterisierung von Distorsionsisomeren der Anionen Pentacyano-oxo-molybdat(IV) sowie Tetracyano-oxo-aqua-molybdat(IV) im festen Zustand. Kristallstrukturen von [(C6H5)4P]3[MoO(CN)5] · 7 H2O(grün), [(C6H5)4As]2 [MoO(OH2)(CN)4] · 4 H2O (blau) und [(C6H5)4P]2[MoO(OH2)(CN)4] · 4 H2O (grün)

Characterization of Distortional Isomers of the Anions Pentacyano-oxo-molybdate(IV) and of Tetracyano-aqua-oxo-molybdate(IV) in the Solid State. Crystal Structures of [(C₆H₅)₄P]₃[MoO(CN)₅] · 7 H₂O (green), [(C₆H₅)₄As]₂[MoO(OH₂)(CN)₄] · 4 H₂O (blue), and [(C₆H₅)₄P]₂[MoO(OH₂) (CN)₄] · 4 H₂O (green) Preparation of a series of salts containing the new pentacyano-oxo-molybdate(IV) anion is described: Cs₂H[MoO(CN)₅] (blue), [(CH₃)₄N]₂H[MoO(CN)₅] · 2 H₂O (blue) and [Cr(en)₃] [MoO(CN)₅] · 4 H₂O (green). The green [(C₆H₅)₄P]₃[MoO(CN)₅] · 7 H₂O crystallizes triclinic in the space group P1 . The molybdenum(IV) center is in an pseudo-octahedral environment of a terminal oxo-group (d(Mo?O); 1.705(4) Å), a CN^? group in the trans-position (d(Mo? C): 2.373(6) Å), and four equatorial CN^? groups (averaged d(Mo? C): 2.178 (Å). The blue and green salts exhibit v(Mo?O) stretching frequencies at 948 cm^?1 and 920 cm^?1, respectively. Blue and green salts containing the [MoO(OH₂)(CN)₄]^2? anion and [(C₆H₅)₄P]⁺ or [(C₆H₅)₄As]⁺ cations have been prepared and characterized by single crystal crystallography. [(C₆H₅)₄P]₂[MoO(OH₂)(CN)₄] · 4 H₂O (green) and [(C₆H₅)₄As]₂[MoO(OH₂)(CN)₄] · 4 H₂O (blue) crystallize monoclinic in the space group C—P2₁/n. They are considered to be distortional isomers of the complex anion: the green species has a Mo?O bond distance of 1.72(2) Å whereas for the blue species d(Mo?O) = 1.60(2) Å is found; the corresponding v(Mo?O) frequencies are at 920 cm^?1 and 980 cm^?1.     

Synthese und Molekülstruktur von [{Cp′(μ‐η1 : η5‐C5H3Me)Mo(μ‐AlRH)}2] (Cp′ = C5H4Me,R = iBu,Et)

Synthesis and Molecular Structure of [{Cp′(μ‐η¹ : η⁵‐C₅H₃Me)Mo(μ‐AlRH)}₂] (Cp′ = C₅H₄Me, R = ⁱBu, Et) [Cp′₂MoH₂] reacts with HAlR₂ to give [{Cp′(μ‐η¹ : η⁵‐C₅H₃Me)Mo(μ‐AlRH)}₂] (Cp′ = C₅H₄Me, R = ⁱBu ( 1 ), Et ( 2 )). Crystal structure determinations were carried out on [Cp′₂MoH₂] and 1 . 1 exhibits a direct Mo–Al bond (2.636(2) Å).     

Synthese und Struktur von [(Ph3C6H2)Te]2, [(Ph3C6H2)Te(AuPPh3)2]PF6 und [(Ph3C6H2)TeAuI2]2

Synthesis and Structure of [(Ph₃C₆H₂)Te]₂, [(Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ and [(Ph₃C₆H₂)TeAuI₂]₂ [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with Ph₃PAu⁺ to yield [2,4,6-Ph₃C₆H₂TeAuPPh₃₂]PF₆ which can be oxidized by I₂ to form the gold(III) complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂. [(2,4,6-Ph₃C₆H₂)Te]₂ crystallizes in the monoclinic space group P2₁/c with a = 810.6(2); b = 2026.5(5); c = 2260.6(7) pm; β = 99.23(3)° and Z = 4. In the crystal structure the ditelluride exhibits a dihedral angle C11? Te1? Te2? C21 of 66.1(2)°. The distance Te1? Te2 is 269.45(6) pm. In the cation of the triclinic complex [(2,4,6-Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ (space group P1 ; a = 1197.4(3); b = 1457.2(4); c = 1680.0(6) pm; α = 84.69(3)°; β = 85.11(3)°; γ = 75.54(3)°; Z = 2) a pyramidal skeleton RTeAu₂ with distances Te? Au = 259.2(1) and 257.8(2) pm and Au? Au = 295.3(1) pm is present. [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ crystallizes in the triclinic space group P1 with a = 1086.3(3); b = 1462.9(6); c = 1654.2(2) pm; α = 85.25(2)°; β = 87.44(1)°; γ = 80.90(3)°; Z = 2. In the centrosymmetrical dinuclear complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ the Au atoms exhibit a square-planar coordination by two iodine atoms and two tellurolate ligands. The tellurolate ligands form symmetrical bridges with distances Te? Au = 260.0 pm. The distances Au? I are in the range of 260.3(1) and 263.7(1) pm.     

Synthese,Struktur und Reaktivität von η3‐1,2‐Diphosphaallylkomplexen sowie von [{(η5‐C5H5)(CO)2W–Co(CO)3}{μ‐AsCH(SiMe3)2}(μ‐CO)]

Syntheses, Structure and Reactivity of η³‐1,2‐Diphosphaallyl Complexes and [{(η⁵‐C₅H₅)(CO)₂W–Co(CO)₃}{μ‐AsCH(SiMe₃)₂}(μ‐CO)] Reaction of ClP=C(SiMe₂iPr)₂ ( 3 ) with Na[Mo(CO)₃(η⁵‐C₅H₅)] afforded the phosphavinylidene complex [(η⁵‐C₅H₅)(CO)₂Mo=P=C(SiMe₂iPr)₂] ( 4 ) which in situ was converted into the η¹‐1,2‐diphosphaallyl complex [η⁵‐(C₅H₅)(CO)₂Mo{η³‐tBuPPC(SiMe₂iPr)₂] ( 6 ) by treatment with the phosphaalkene tBuP=C(NMe₂)₂. The chloroarsanyl complexes [(η⁵‐C₅H₅)(CO)₃M–As(Cl)CH(SiMe₃)₂] [where M = Mo ( 9 ); M = W ( 10 )] resulted from the reaction of Na[M(CO)₃(η⁵‐C₅H₅)] (M = Mo, W) with Cl₂AsCH(SiMe₃)₂. The tungsten derivative 10 and Na[Co(CO)₄] underwent reaction to give the dinuclear μ‐arsinidene complex [(η⁵‐C₅H₅)(CO)₂W–Co(CO)₃{μ‐AsCH(SiMe₃)₂}(μ‐CO)] ( 11 ). Treatment of [(η⁵‐C₅H₅)(CO)₂Mo{η³‐tBuPPC(SiMe₃)₂}] ( 1 ) with an equimolar amount of ethereal HBF₄ gave rise to a 85/15 mixture of the saline complexes [(η⁵‐C₅H₅)(CO)₂Mo{η²‐tBu(H)P–P(F)CH(SiMe₃)₂}]BF₄ ( 18 ) and [Cp(CO)₂Mo{F₂PCH(SiMe₃)₂}(tBuPH₂)]BF₄ ( 19 ) by HF‐addition to the PC bond of the η³‐diphosphaallyl ligand and subsequent protonation ( 18 ) and/or scission of the PP bond by the acid ( 19 ). Consistently 19 was the sole product when 1 was allowed to react with an excess of ethereal HBF₄. The products 6 , 9 , 10 , 11 , 18 and 19 were characterized by means of spectroscopy (IR, ¹H‐, ¹³C{¹H}‐, ³¹P{¹H}‐NMR, MS). Moreover, the molecular structures of 6 , 11 and 18 were determined by X‐ray diffraction analysis.     

Bis(arylimido) Molybdenum(VI) Amidinate and Guanidinate Complexes; Molecular Structures of [(ArN)2MoMe{N(Cy)C[N(i‐Pr)2]N(Cy)}] (Ar = 2,6‐i‐Pr2C6H3; Cy = Cyclohexyl) and [(2,6‐i‐Pr2C6H3N)2MoCl2] · [NH=C(C6H5)CH(SiMe3)2]

The reaction of [(ArN)₂MoCl₂] · DME (Ar = 2,6‐i‐Pr₂C₆H₃) ( 1 ) with lithium amidinates or guanidinates resulted in molybdenum(VI) complexes [(ArN)₂MoCl{N(R¹)C(R²)N(R¹)}] (R¹ = Cy (cyclohexyl), R² = Me ( 2 ); R¹ = Cy, R² = N(i‐Pr)₂ ( 3 ); R¹ = Cy, R² = N(SiMe₃)₂ ( 4 ); R¹ = SiMe₃, R² = C₆H₅ ( 5 )) with five coordinated molybdenum atoms. Methylation of these compounds was exemplified by the reactions of 2 and 3 with MeLi affording the corresponding methylates [(ArN)₂MoMe{N(R¹)C(R²)N(R¹)}] (R¹ = Cy, R² = Me ( 6 ); R¹ = Cy, R² = N(i‐Pr)₂ ( 7 )). The analogous reaction of 1 with bulky [N(SiMe₃)C(C₆H₅)C(SiMe₃)₂]Li · THF did not give the corresponding metathesis product, but a Schiff base adduct [(ArN)₂MoCl₂] · [NH=C(C₆H₅)CH(SiMe₃)₂] ( 8 ) in low yield. The molecular structures of 7 and 8 are established by the X‐ray single crystal structural analysis.     

[CpR(OC)Mo(μ‐η2:2‐P2)2FeCpR′] als Edukt für heterobimetallische Zweikerncluster mit P2‐ und CnRnP4‐n‐Liganden (n = 1, 2)

[Cp^R(OC)Mo(μ‐η^2:2‐P₂)₂FeCp^R′] as Educt for Heterobimetallic Dinuclear Clusters with P₂ and C_nR_nP_4‐n Ligands (n = 1, 2) The cothermolysis of [Cp^R(OC)Mo(μ‐η^2:2‐P₂)₂FeCp^R′] ( 1 ) and tBuC≡P ( 2 ) as well as PhC≡CPh ( 3 ) affords the heterobimetallic triple‐decker like dinuclear clusters [(Cp'''Mo)(Cp*′Fe)(P₃CtBu)(P₂)] ( 4 ), Cp''' = C₅H₂tBu₃‐1,2,4, Cp*′ = C₅Me₄Et, and [(Cp*Mo)(Cp*Fe)(P₂C₂Ph₂)(P₂)] ( 5 ) with a bridging tri‐ and diphosphabutadiendiyl ligand. 4 and 5 have been characterized additionally by X‐ray crystallography.     

Synthese,Struktur und Eigenschaften von [(C4H9)2NH2]4[Sn2Se6], [(C4H9)2NH2]4[Sn4Se10] · 2 H2O und [(C3H7)3NH]2[Sn3Se7]

About Selenidostannates. I Synthesis, Structure, and Properties of [Sn₂Se₆]^4–, [Sn₄Se₁₀]^4–, and [Sn₃Se₇]^2– The selenidostannates [(C₄H₉)₂NH₂]₄Sn₂Se₆ · H₂O ( I ), [(C₄H₉)₂NH₂]₄Sn₄Se₁₀ · 2 H₂O ( II ) und [(C₃H₇)₃NH]₂Sn₃Se₇ ( III ) were prepared by hydrothermal syntheses from the elements and the amines. I crystallizes in the monoclinic spacegroup P2₁/n (a = 1262.9(3) pm, b = 1851.3(4) pm, c = 2305.2(4) pm, β = 104.13(3)° and Z = 4). The [Sn₂Se₆]^4– anion consists of two edge‐sharing tetrahedra. II crystallizes in the orthorhombic spacegroup Pna2₁ (a = 2080.3(4) pm, b = 1308.2(3) pm, c = 2263.5(5) pm and Z = 4). The anion is formed from four SnSe₄ tetrahedra which are joined by common corners to the adamantane cage [Sn₄Se₁₀]^4–. III crystallizes in the orthorhombic spacegroup Pbcn (a = 1371.1(3) pm, b = 2285.4(5) pm, c = 2194.7(4) pm and Z = 8). The anion is a chain, built from edge‐sharing [Sn₃Se₅Se_4/2]^2– units, in which two corner sharing tetrahedra are connected to a trigonal bipyramid by an edge of one and a corner of the other tetrahedron. The results of the TG/DSC measurements and of temperature dependent X‐ray diffractograms reveal that I and II decompose at first by release of minor quantities of triethylammonium to compounds with layer structure and larger cell dimensions. At still higher temperature the rest of triethylammonium and H₂Se is evolved, leaving SnSe₂ and Se in the bulk. The former decomposes partially at the highest temperature to SnSe. In the measurements of III the complex intermediate compound was not observed. III decomposes directly to SnSe₂.     

Addition von kationischen Lewis‐Säuren [M′Ln]+ (M′Ln = Fe(CO)2Cp,Fe(CO)(PPh3)Cp,Ru(PPh3)2Cp,Re(CO)5, ${1 \over 2}$ Pt(PPh3)2, W(CO)3Cp an die anionischen Thiocarbonyl‐Komplexe [HB(pz)3(OC)2M(CS)]− (M = Mo,W; pz = 3,5‐dimethylpyrazol‐1‐yl)

Addition of Cationic Lewis Acids [M′L_n]⁺ (M′L_n = Fe(CO)₂Cp, Fe(CO)(PPh₃)Cp, Ru(PPh₃)₂Cp, Re(CO)₅, Pt(PPh₃)₂, W(CO)₃Cp to the Anionic Thiocarbonyl Complexes [HB(pz)₃(OC)₂M(CS)]⁻ (M = Mo, W; pz = 3,5‐dimethylpyrazol‐1‐yl) Adducts from Organometallic Lewis Acids [Fe(CO)₂Cp]⁺, [Fe(CO)(PPh₃)Cp]⁺, [Ru(PPh₃)₂Cp]⁺, [Re(CO)₅]⁺, [ Pt(PPh₃)₂]⁺, [W(CO)₃Cp]⁺ and the anionic thiocarbonyl complexes [HB(pz)₃(OC)₂M(CS)]⁻ (M = Mo, W) have been prepared. Their spectroscopic data indicate that the addition of the cations occurs at the sulphur atom to give end‐to‐end thiocarbonyl bridged complexes [HB(pz)₃(OC)₂MCSM′L_n].     

Cleavage of the Fe—Fe Bond of （Me2SiSiMe2） [η^5－C5H4Fe（CO）2]2 with Na／Hg and Molecular Structure of the Ring－Opened Complex

The reaction of the rifle cyclic complex (1) with sodium amalgam in THF resulted in the expected cleavage of the Fe-Fe bond to afford his-sodium salt ( Me2SiSiMe2 ) [η^5-C5H4Fe(CO)2]2 (4). The latter was not isolated and was used directly to react with MeI, PhCH2Cl, CH3C(O)Cl, PhC(O)Cl,Cy3SnCl (Cy= cyclohexyl) or Ph3SnCl to afford corresponding ring-opened derivatives (Me2SiSiMe2) [η^5-C5H4Fe(CO)2]2 [5, R=Me; 6, R=PhCH2; 7, R=CH3C(O); 8, R=PhC(O); 9, R = Cy3Sn or 10, R = Ph3Sn ]. The crystal and molecular structures of 10 were determined by X-ray diffraction analysis. The molecule took the desired ant/ conformation around the Si-Si bond. The length of the Si--Si bond is 0.2343(3)nm, which is essentially identical to that in the cyclic structure of 1[0.2346(4) tun]. This result unambiguously demonstrates that the Si--Si bond in the cyclic structure of 1 is not subject to obvious strain.     

(Carbonyl)Iron‐Selenolates: New Synthetic Methods and Reactions with Electrophiles. Crystal Structures of [(CO)6Fe2(μ‐SeR)2]; R = Me3SiCH2 and p‐O2NC6H4CH2, {(CO)6Fe2[μ‐η2‐Se,Se′‐o‐(SeCH2C6H4CH2Se)]}, and [(CO)6Fe2(μ‐SeFe(CO)2cp)2]

The reactions of Fe(CO)₅ or Fe₃(CO)₁₂ with NaBEt₃H or KB[CH(CH₃)C₂H₅]₃H, respectively and treatment of the resulting carbonylates M₂Fe(CO)₄, M = Na, K with elemental selenium in appropriate ratios lead to the formation of M₂[Fe₂(CO)₆(μ‐Se)₂]. Subsequent reactions with organo halides or the complex fragment cpFe(CO)₂⁺, cp = η⁵‐C₅H₅ afforded the selenolato complexes [Fe₂(CO)₆(μ‐SeR)₂], R = CH₂SiMe₃ ( 1 ), CH₂Ph ( 2 ), p‐CH₂C₆H₄NO₂ ( 3 ), o‐CH₂C₆H₄CH₂ ( 4 ) and cpFe(CO)₂⁺ ( 5 ) in moderate to good yields. A similar reaction employing Ru₃(CO)₁₂, Se and p‐O₂NC₆H₄CH₂Br leads to the formation of the corresponding organic diselenide. The X‐ray structures of 1 , 3 , 4 and 5 were determined and revealed butterfly structures of the Fe₂Se₂ cores. The substituents in 1 , 3  and 5 adopt different conformations depending on their steric demand. In 4 , the conformation is fixed because of the chelate effect of the ligand. The Fe–Se bond lengths lie in the range 235 to 240 pm, with corresponding Fe–Fe bond lengths of 254 to 256 pm. The ⁷⁷Se NMR data of the new complexes are discussed and compared with the corresponding data of related complexes.     

Preparation of new (η5-C5H4CH3)Mn(NO)(PPh3) and (η7-C7H7)Mo(CO)-(PPh3) complexes

The complex (η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)I has been prepared by the reaction of NaI with [(η⁵-C₅H₄CH₃)Mn(NO)(CO)(PPh₃)]⁺ and also by the reaction of [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ with NaI followed by PPh₃. This iodide compound reacts with NaCN to yield (η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)CN which is ethylated by [(C₂H₅)₃O]BF₄ to yield [(η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)(CNC₂H₅)]⁺. Both [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ and [(η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)(CO)]⁺ react with NaCN to yield [(η⁵-C₅H₄CH₃)Mn(NO)(CN)₂]^?. This anion reacts with Ph₃SnCl to yield cis-(η⁵-C₅H₄CH₃)Mn(NO)(CN)₂SnPh₃ and with [(C₂-H₅)₃O]BF₄ to yield [(η⁵-C₅H₄CH₃)Mn(NO)(CNC₂H₅)₂]⁺. The reaction of (η⁵-C₅-H₄CH₃)Mn(NO)(PPh₃)I with AgBF₄ in acetonitrile yields [(η⁵-C₅H₄CH₃)Mn-(NO)(PPh₃)(NCCH₃)]⁺. The complex (η⁵-C₅H₄CH₃)Mn(NO)(CO)I, produced in the reaction of [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ with NaI, is not stable and decomposes to the dimeric complex (η⁵-C₅H₄CH₃)₂Mn₂(NO)₃I for which a reasonable structure is proposed. Similar dimers can be prepared from the other halide salts. The reaction of (η⁷-C₇H₇)Mo(CO)(PPh₃)I with NaCN yields (η⁷-C₇-H₇)Mo(CO)(PPh₃)CN which is ethylated by [(C₂H₅)₃O]BF₄ to yield [(η⁷-C₇H₇)-Mo(CO)(PPh₃)(CNC₂H₅)]⁺. The interaction of this molybdenum halide complex with AgBF₄ in acetonitrile and pyridine yields [(η⁷-C₇H₇)Mo(CO)(PPh₃)-(NCCH₃)]⁺ and [(η⁷-C₇H₇)Mo(CO)(PPh₃)(NC₅H₅)]⁺, respectively. Both (η⁵-C₅-H₄CH₃)Mn(NO)(PPh₃)I and (η⁷-C₇H₇)Mo(CO)(PPh₃)I are oxidized by NOPF₆ to the respective 17-electron cations in acetonitrile at ?78°C but revert to the neutral halide complex at room temperature. This result is supported by electrochemical data.     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

Die Reaktion von tBu2P‐P=P(Me)tBu2 mit [Fe2(CO)9] und [(η2‐C8H14)2Fe(CO)3]

^tBu₂P‐P=P(Me)^tBu₂ reacts with [Fe₂(CO)₉] to give [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₃}{Fe(CO)₄}] ( 1 ) and [trans‐(^tBu₂MeP)₂Fe(CO)₃]( 2 ). With [(η²‐C₈H₁₄)₂Fe(CO)₃] in addition to [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₂PMe^tBu₂}‐{Fe(CO)₄}] ( 10 ) and 2 also [(μ‐P^tBu₂){μ‐P‐Fe(CO)₃‐PMe^tBu₂}‐{Fe(CO)₃}₂(Fe‐Fe)]( 9 ) is formed. 1 crystallizes in the monoclinic space group P2₁/c with a = 875.0(2), b = 1073.2(2), c = 3162.6(6) pm and β = 94.64(3)?. 2 crystallizes in the monoclinic space group P2₁/c with a = 1643.4(7), b = 1240.29(6), c = 2667.0(5) pm and β = 97.42(2)?. 9 crystallizes in the monoclinic space group P2₁/n with a = 1407.5(5), b = 1649.7(5), c = 1557.9(16) pm and β = 112.87(2)?.