Addition des O'Donnell Reagenzes [Ph2C=NCHCO2Me]– an π-koordinierte,ungesättigte Kohlenwasserstoffe in [(C6H7)Fe(CO)3]+, [(C7H9)Fe(CO)3]+, [(C7H7)M(CO)3]+ (M = Cr,Mo) und [(C2H4)Re(CO)5]+. α-Aminosäuren mit metallorganischen Seitenketten

Metal Complexes of Biologically Important Ligands. CXVII [1] Addition of the O'Donnell Reagent [Ph₂C=NCHCO₂Me]^– to Coordinated, Unsaturated Hydrocarbons of [(C₆H₇)Fe(CO)₃]⁺, [C₇H₉Fe(CO)₃]⁺, [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo), and [(C₂H₄)Re(CO)₅]⁺. α-Amino Acids with Organometallic Side Chains The addition of [Ph₂C=NCHCO₂Me]^– to [(C₆H₇)Fe(CO)₃]⁺, [(C₇H₉)Fe(CO)₃]⁺, [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo) and [(C₂H₄)Re(CO)₅]⁺ gives derivatives of α-amino acids with organometallic side chains. The structure of [(η⁴-C₆H₇)CH(N=CPh₂)CO₂Me]Fe(CO)₃ was determined by X-ray diffraction. From the adduct of [Ph₂C=NCHCO₂Me]^– and [(C₇H₇)Mo(CO)₃]⁺ the Schiff base of a new unnatural α-amino acid, Ph₂C=NCH(C₇H₇)CO₂Me, was obtained.     

Photochemical reactions of (CO)2 (PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3

Conclusions The photochemical reactions of (CO)₂(PPh₃)MnC₅H₄Fe(CO)₂C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)₂C₅H₅ with PPh₃ gave the products of replacing the CO on the Fe atom by PPh₃: respectively (CO)₂(PPh₃)MnC₅H₄Fe (CO)(PPh₃)C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)(PPh₃)C₅H₅.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2813–2815, December, 1977.     

Derivative des borols: VI. Dehydrierende komplexierung von borolenen mit carbonylmetallen: (borol)metall-komplexe von mangan,eisen und cobalt

The reaction of 2-borolenes and 3-borolenes C₄H₆BR (R = Ph, Me, C₆H₁₁, OMe) with Mn, Fe, and Co carbonyls leads to dehydrogenating complexation with formation of simple, i.e. C-unsubstituted (η⁵-borole)metal complexes. Thus, Mn₂(CO)₁₀ gives the triple-decked complexes (μ-η⁵-C₄H₄BR)[Mn(CO)₃]₂ (R = Ph, OMe). By irradiation of Fe(CO)₅ the half-sandwich complexes Fe(CO)₃ (η⁵-C₄H₄BR) (R = Ph, Me, C₆H₁₁, OMe) are formed, whereas Co₂(CO)₈ yields the dinuclear complexes (μ-CO)₂[Co(CO)(η⁵-C₄H₄BR)]₂ (Co-Co) (R = Ph, Me). A low-temperature X-ray structure determination of Fe(CO)₃(η⁵-C₄H₄BPh) is described in detail.     

Stoichiometric vs Catalytic MeLi Reaction with the Mixture of (ẽ5‐C5H5)Fe(CO)2l and P(OR)3: Nucleophilic Methylation vs Arbuzov‐Like Dealkylation

The reaction of stoichiometric MeLi with the 1:1 mixture of (?⁵‐C₅H₅)Fe(CO)₂I/P(OR)₃ (R = Me, Et, and Ph) at ?78°C changes the bonding mode between metal and ring from (?⁵‐C₅H₅) to (?⁴‐exo‐MeC₅H₅) and the oxidation state of metal from Fe(II) to Fe(O), the novel complexes (?⁴‐exo‐MeC₅H₅)Fe(CO)₂P(C)R)₃ being obtained in 45‐57% yields. The reaction of trace MeLi with the 1:1 mixture of (?⁵‐C₅H₅)Fe(CO)₂I/P(OMe)₃ at ?78°C results in 70% yield of the phosphonate complex (?⁵‐C₅H₅)Fe(CO)₂P(O)(OMe)₂ which is an Arbuzov‐like dealkylation product from the cationic intermediate [(?⁵‐C₅H₅)Fe(CO)₂P(OMe)₃⁺] and the iodide. The amines could assist the Arbuzov‐like dealkylation of [(?⁵‐C₅H₅)Fe(CO)₂P(OMe)₃⁺] [PF₆^?] where iron‐carbamoyl intermediates are likely involved in the case of primary amines.     

Isocyanide addition to MN2(CO)5(Ph2PCH2PPh2)2 and the formation of a four-electron doubly-bridging isocyanide

The reactions of Fe(CO)₅, Fe(CO)₄P(C₆H₅)₃, M(CO)₆ (M  W, Mo, Cr), and (CH₃C₅H₄Mn(CO)₃ with KH and several boron and aluminium hydrides were investigated. Iron pentacarbonyl was converted quantitatively to K⁺Fe(CO)₄-(CHO) by hydride transfer from KBH(OCH₃)₃ allowing isolation of [P(C₆H₅)₃]₂-Nⁿ⁺Fe(CO)₄(CHO)^? in 50% yield. Lower yields were obtained with LiBH(C₂H₅)₃, and other hydride sources gave little or no formyl product. The stability of Fe(CO)₄(CHO)^? in THP was found to depend on the cation, decreasing in the order [P(C₆H₅)₃]₂N⁺ > K⁺ > Na⁺ > Li⁺. No formyl complexes were isolated and no spectroscopic evidence for formyl formation was observed in the reactions of the other transition metal carbonyls with several hydride sources. Fe(CO)₄-P(C₆H₅)₃ gave K₂Fe(CO)₄ when treated with KHB(OCH₃)₃. When treated with LiBH(C₂H₅)₃, W(CO)₆ gave a mixture of HW₂(CO)₁₀^?and (OC)₅W(COC₂H₅)^?; the latter was methylated to give the carbene complex (OC)₅WC(OCH₃)C₂H₅.     

Synthesis and molecular structures of heterometallic complexes [RC5H4Fe(CO)2]2 Sn(TePh)2 and their adducts with chromium and tungsten carbonyls or with trimethylplatinum iodide

Complexes [RC₅H₄Fe(CO)₂]₂Sn(TePh)₂ (R=H, Me) containing stable heterometallic Fe−Sn−Fe fragments with two phenyltellurium groups at the tin atom were synthesized from [RC₅H₄Fe(CO)₂]₂SnCl₂ (R=H, Me) and sodium phenyltelluride and their structures were established by X-ray analysis. Their chelates with tungsten tetracarbonyl, [RC₅H₄Fe(CO)₂]₂Sn(TePh)₂[W(CO)₄] (R=Me, H), and complexes with two Cr(CO)₅ fragments or dimeric trimethylplatinum iodide were synthesized and studied by X-ray analysis. Thermal decomposition of [RC₅H₄Fe(CO)₂]₂Sn(TePh)₂ complexes and their adducts with ML fragments (ML=W(CO)₄, 2 Cr(CO)₅, (Me₃PtI)₂) into inorganic tellurides of a preset mixed-metal—chalcogenide composition was studied by differential scanning calorimetry. The temperature of complete elimination of organic fragments from methylcyclopentadienyl complexes is about 100°C lower than in the case of cyclopentadienyl analogs. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1766–1772, September, 1999.     

Cyclopentadienyleisen-komplexe mit P(OR)3-liganden; Synthese und spektroskopische charakterisierung

Reactions of reactive cyclopentadienyliron complexes C₅H₅Fe(CO)₂I, [C₅H₅Fe(CO)₂THF]BF₄, [C₅H₅Fe(CO)((CH₃)₂S)₂]BF₄ and [C₅H₅Fe(p-(CH₃)₂C₆H₄)]PF₆ with P(OR)₃ as ligands (R = CH₃, C₂H₅, i-C₃H₇ and C₆H₅) lead to the formation of the complex compounds C₅H₅Fe(CO)_2?n(P(OR)₃)_nI and [C₅H₅Fe(CO)_3?n(P(OR)₃)_n]X (n = 1, 2 and n = 1–3, X = BF₄, PF₆). Spectroscopic investigations (IR, ¹H, ¹³C and ³¹P NMR) indicate an increase of electron density on the central metal with increasing substitution of CO groups by P(OR)₃ ligands. The stability of the compounds increase in the same way.     

Preparation and reactivity of the new cyclopentadienyl-bridged complex (Me2SiCH2CH2SiMe2)(C5H4Fe(CO)2)2

A new metal-metal bonded binuclear iron system [Me₂SiCH₂CH₂SiMe₂][η⁵-C₅H₄Fe(CO)₂]₂ (2) has been prepared by treating two equivalents of NaCp with one equivalent of ClSi(Me)₂CH₂CH₂SiClMe₂ obtaining the intermediate (C₅H₅)Si(Me)₂CH₂CH₂Si(Me)₂(C₅H₅) which then is directly allowed to react with Fe(CO)₅ given 2 in 30% yield. From this cyclopentadienyldisilyl linked system three new binuclear irom complexes are formed. Treatment of 2 with Na/Hg in THF produced the dianion [Me₂SiCH₂CH₂SiMe₂][η⁵-C₅H₄Fe(CO)₂^?]₂ which is quenched with CH₃I giving [Me₂SiCH₂CH₂SiMe₂][η⁵-C₄H₄Fe(CO)₂CH₃]₂ (4) in 76% yield. Complex 2 is oxidized with 1.2 equivalent of I₂ to give [Me₂SiCH₂CH₂SiMe₂][η⁵-C₅H₄Fe(CO)₂I]₂ (5) in 85% yield. Photolysis of 5 (1 equiv.) and PPh₃ (3 equiv.) results in the formation of the bis-substituted compound [Me₂SiCH₂CH₂SiMe₂][η⁵-C₅H₄Fe(CO)(PPh₃)I]₂ (6). These four new binuclear iron complexes are characterized by ¹H, ¹³C, and ³¹P NMR and IR spectroscopy.     

Die Strukturen der 1,3,5-Trisilacyclohexan-Eisendicarbonyl-cyclopentadienylkomplexe C3H6Si3Cl5Fe(CO)2πcp und C3H6Si3Cl4(Fe(CO)2πcp)2

Structures of the l,3,5-Trisilacyclohexane-Iron Dicarbonyl-cyclopentadienyl Complexes and C₃H₆Si₃Cl₅Fe(CO)₂πcp and C₃H₆Si₃Cl₄(Fe(CO₂)πcp)₂ Trisilapentachlorocyclo-hexyl-dicarbonylcyclopentadienyliron C₃H₆Si₃Cl₅Fe(CO)₂πcp 1 and Trisilatetrachlorocyclohexyl-bis(dicarboncyclopentadienyliron)C₃H₆Si₃Cl₄(Fe(CO)₂πcp)₂ 2 are 1,3,5-Trisilacyclohexane complexes substituted by dicarbonylcyclopentadienyliron at one and two silicon atoms of the six-membered ring, respectively. The crystal and molecular structures were determined from single crystals ( 1 ; space group P2₁/a (No. 14); a = 1100.5 pm; b = 2033.9 pm; c = 843.3pm; β = 98.58°; Z = 4; MoKα-radiation; 3142h k l; R = 0.036. 2 ; space group P1 ; (No. 2); a = 1231.1 pm; b = 1267.3 pm; c = 1045.9 pm; α = 113.23°; β = 83.93°; γ = 115.00°; Z = 2; Mokα-radiation; 4196 h k 1; R = 0.065). In both complexes the six-membered rings of the carbosilane ligands are in skew-boat conformation. The bond lengths Fe? Si are 226.4 pm and 228.1 pm, respectively. The distances Si? C and Si? Cl are 186 pm and 206 pm in 1 and 187 pm and 209 pm in 2 . Their different lengths depend on the position in the ligand system and can be explained with the concept of bond orders.     

Übergangsmetall-Silyl-Komplexe, 44. Darstellung der zweikernigen Silyl-Komplexe (CO)3(R3Si)Fe(μ-PR′R′′)Pt(PPh3)2 durch oxidative Addition von (CO)3(R′R′′HP)Fe(H)SiR3 an (C2H4)Pt(PPh3)2

Transition Metal Silyl Complexes, 44. — Preparation of the Binuclear Silyl Complexes (CO)₃(R₃Si)Fe(μ-PR′R′′)Pt(PPh₃)₂ by Oxidative Addition of (CO)₃(R′R′′HP)Fe(H)SiR₃ to (C₂H₄)Pt(PPh₃)₂ The complexes (CO)₃(R′R′′HP)Fe(H)SiR₃ ( 1 ) [PHR′R′′ = PHPh₂, PH₂Ph, PH₂Cy; SiR₃ = SiPh₃, SiPh₂Me, SiPhMe₂, Si(OMe)₃] react with Pt(C₂H₄)(PPh₃)₂ to give the dinuclear, silyl-substituted complexes (CO)₃(R₃Si)Fe(μ-PR′R′′)Pt(PPh₃)₂ ( 2 ) in high yields. Upon reaction of 2 (R = R′ R′′ = Ph) with CO, the PPh₃ ligand at Pt being trans to the PPh₂ bridge is exchanged, and (CO)₃(Ph₃Si)Fe(μ-PPh₂)Pt(PPh₃)CO ( 3 ) is formed. Complex 3 is characterized by an X-ray structure analysis. The rather short Fe — Si distance [233.9(2) pm] and the infrared spectrum of 3 indicate that the Fe — Pt bond is quite polar.     

(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.     

Darstellung carboxylatsubstituierter Rhenium-Gold-Metallatetrahedrane Re2(AuPPh3)2(μ-PCy2)(CO)7(η1-OC(R)O) (R = H,Me, CF3, Ph, 3,4-(OMe)2C6H3)

Synthesis of Carboxylate Substituted Rhenium Gold Metallatetrahedranes Re₂(AuPPh₃)₂(μ-PCy₂)(CO)₇(η¹-OC(R)O) (R = H, Me, CF₃, Ph, 3,4-(OMe)₂C₆H₃) The reaction of the in situ prepared salt Li[Re₂(μ-H)(μ-PCy₂)(CO)₇(ax-C(Ph)O)] ( 2 ) with 1,5 equivalents of monocarboxylic acid RCOOH (R = H ( 4 a ), Me ( 4 b ), CF₃ ( 4 c ), Ph ( 4 d ), 3,4-(OMe)₂C₆H₃ ( 4 e ) in tetrahydrofruan (THF) solution at 60 °C gives within 4 h under release of benzaldehyde (PhCHO) the η¹-carboxylate substituted dirhenium salt Li[Re₂(μ-H)(μ-PCy₂)(CO)₇(η¹-OC(R)O)] (R = H ( 4 a ), Me ( 4 b ), CF₃ ( 4 c ), Ph ( 4 d ), 3,4-(OMe)₂C₆H₃ ( 4 e )) in almost quantitative yield. The lower the pK_a value of the respective carboxylic acid the faster the reaction proceeds. It was only in the case of CF₃COOH possible to prove the formation of the hydroxycarbene complex Re₂(μ-H)(μ-PCy₂)(CO)₇(=C(Ph)OH) ( 5 ) prior to elimination of PhCHO. The new compounds 4 a–4 e were only characterized by ³¹P NMR and ν(CO) IR spectroscopy as they are only stable in solution. They are converted with two equivalents of BF₄AuPPh₃ at 0 °C in a so-called cluster expansion reaction into the heterometallic metallatetrahedrane complexes Re₂(AuPPh₃)₂(μ-PCy₂)(CO)₇(η¹-OC(R)O) (R = H ( 7 a ), Me ( 7 b ), CF₃ ( 7 c ), Ph ( 7 d ), 3,4-(OMe)₂C₆H₃ ( 7 e )) (yield 47–71% ). The expected precursor complexes of 7 a–7 e Li[Re₂(AuPPh₃)(μ-PCy₂)(CO)₇(η¹-OC(R)O] ( 8 ) were not detected by NMR and IR spectroscopy in the course of the reaction. Their existence was retrosynthetically proved by the reaction of 7 b with an excess of the chelating base TBD (1,5,7-Triazabicyclo[4.4.0]dec-5-en) forming [(TBD)_xAuPPh₃][Re₂(AuPPh₃)(μ-PCy₂)(CO)₇(η¹-OC(Me)O] ( 8 b ) in solution. The η¹-bound carboxylate ligand in 7 a–7 e can photochemically be converted into a μ-bound ligand in Re₂(AuPPh₃)₂(μ-PCy₂)(μ-OC(R)O)(CO)₆ (R = H ( 9 a ), Me ( 9 b ), CF₃ ( 9 c ), Ph ( 9 d ), 3.4-(MeO)₂C₆H₃ ( 9 e )) under release of one equivalent CO. All isolated cluster complexes were characterized and identified by the following analytical methods: elementary analysis, NMR (¹H, ³¹P) spectroscopy, ν(CO) IR spectroscopy and in the case of 7 d and 9 b by X-ray structure analysis.     

Synthesis and X‐ray Crystal Structures of Ru3(CO)9(μ‐arphos)(L) [L = AsPh3, As(m‐C6H4Me)3, As(p‐C6H4Me)3]

Three new triruthenium clusters, Ru₃(CO)₉(μ‐arphos)AsPh₃ ( 1 ), Ru₃(CO)₉(μ‐arphos)As(m‐C₆H₄Me)₃ ( 2 ), and Ru₃(CO)₉(μ‐arphos)As(p‐C₆H₄Me)₃ ( 3 ) were synthesized via thermal reactions of Ru₃(CO)₁₀(μ‐arphos) with different tertiary arsine ligands [AsPh₃, As(m‐C₆H₄Me)₃, As(p‐C₆H₄Me)₃]. All these complexes were fully characterized by elemental analysis, FT‐IR, NMR spectroscopy, and single‐crystal X‐ray diffraction.     

Nitrosyl derivatives of tricobaltcarbon clusters

The nitrosyl clusters PPN[YCCo₃(CO)₇(NO)] (Y = Me, Ph, COOH, (C₅H₅)Fe(C₅H₄)) have been prepared in high yield from the reaction of YCCo₃(CO)₉ with PPN(NO₂) in THF, acetone or acetonitrile. Spectroscopic evidence indicates the structure of the nitrosyl anions is derived from that of YCCo₃(CO)₉ by the replacement of two CO ligands on one cobalt atom by a linear, terminal nitrosyl group. The nitrosyl metallates are extremely sensitive to oxidation and attempts to protonate the anions resulted in the reformation of the parent YCCo₃(CO)₉, molecules. The oxidative electrochemistry of the ferrocene complex, PPN[(C₅H₅)Fe(C₅H₄CCo₃(CO)₇(NO)] is also discussed.     

Metal dimers as catalysts : III. The reaction between Fe(CO)5, and group V donor ligands in the presence of [(η5-C5H4R)Fe(CO)222]2 (R  H,Me) and [(η5-C5Me5)Fe(CO)2]2 as catalyst

The reaction between Fe(CO)₅, and group V donor ligands L, (L  PPh₃, AsPh₃, SbPh₃, PMePh₂, PMe₂Ph, Asme₂Ph, P(C₆H₁₁)₃, P(n-Bu)₃, P(i-Bu)₃, P(OPh)₃, P(OEt)₃, P(OMe)₃) in the presence of [(η⁵-C₅Me₅Fe(CO)₂]₂ (R  H, Me) or [(η⁵-C₅Me₅)Fe(CO)₂]₂ as catalyst in refluxing toluene, rapidly gives the complexes Fe(CO)₄L in yields > 85%. The reaction rate is essentially independent of the nature of L for [(η₅-C₅Me₅)Fe(CO)₂]₂ as catalyst. For the other catalysts, the rate is influenced predominantly by the steric properties of L. These results are interpreted in terms of the interaction between the catalyst and the ligand L to give derivatives of the type (η⁵-C₅H₄R)₂Fe₂,(CO)₃,(L). These derivatives were also found to catalyse the reaction between Fe(CO)₅, and L. The complexes [(η-C₅H₄R)Fe(CO)₂]₂ (R  H, Me) and [(η⁵-C₅Me₅)Fe(CO)₂]₂ also catalyse the reaction between Mn₂(CO)₁₀ and PPh₃ to give Mn₂(CO)₈- PPh₃)₂ in > 80% yield.     

Mass spectrometry of metal compounds: II—mass spectrometric studies of [CF3EMn(CO)4]2, [CF3EFe(CO)3]2 (E = S,Se), CF3SeFe(CO)2C5H5 and CF3SCr(NO)2C5H5

The electron impact induced mass spectra of [CF₃SMn(CO)₄]₂, [CF₃SeMn(CO)₄]₂, [CF₃SFe(CO)₃]₂, [CF₃SeFe(CO)₃]₂, CF₃SeFe(CO)₂C₅H₅ and CF₃SCr(NO)₂C₅H₅ are reported. These compounds exhibit weak molecular ion peaks and undergo preferential loss of CO or NO groups. The CO or NO free fragments suffer typical loss of ECF₂(E = S, Se) with the simultaneous shift of F from carbon to metal. The ions [FFeC₅H₅]⁺ and [FCrC₅H₅]⁺ in the spectra of the cyclopentadienyl compounds prefer expulsion of π-cyclopentadienyls. The pyrolysis effects on the spectra of the compounds have been studied. An increase in temperature eases the expulsion of ECF₂ groups from all the compounds and favors the formation of [Fe(C₅H₅)₂]⁺ and [Cr(C₅H₅)₂]⁺ in the cyclopentadienyl compounds.     

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.     

1,2-Diphosphaferrocene als Liganden in Übergangsmetallkomplexen. Röntgenstrukturanalyse von [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}]

1,2-Diphosphaferrocenes as Ligands in Transition Metal Complexes. X-Ray Structure Analysis of [(η⁵-1,3-tBu₂C₅H₃){η⁵-1,2-[Co₂(CO)₆]-3,4-(Me₃SiO)₂-5-(Me₃Si)P₂C₃}] Reaction of metallo-1,2-diphosphapropene (η⁵-tBuC₅H₄)(CO)₂Fe? P(SiMe₃)? P?C(SiMe₃)₂ with (Z-cyclooctene)Cr(CO)₅ afforded the pentacarbonylchromium adduct of a 1,2-diphosphaferrocene [(η⁵-tBuC₅C₅H₄){η⁵-1-[Cr(CO)₅]-3,4-(Me₃SiO)₂-5-(Me₃Si)P₂C₃}Fe] ( 1 c ). Diphosphaferrocene [(η⁵-tBuC₅H₄){η⁵-3,4-(Me₃SiO)₂-5-(Me₃Si)P₂C₃}Fe] ( 2 c ) was formed when (η⁵-tBuC₅H₄)(CO)₂FeBr was treated with (Me₃Si)₂P? P?C(SiMe₃)₂ in toluene at 60°C. Photolysis of molybdenum- and tungsten hexacarbonyl in the presence of [(η⁵-1,3-tBu₂C₅H₃){η⁵-3,4-(Me₃SiO)₂-5-(Me₃Si)P₂C₃}Fe] ( 2 b ) gave the pentacarbonylmetal adducts 8 (M = Mo) and 9 (M = W), respectively. A corresponding manganese derivative resulted from the photochemical reaction of 2 b and (MeC₅H₄)Mn(CO)₃. Treatment of 2 b with Co₂(CO)₈ yielded trinuclear [(η⁵-1,3-tBu₂C₅H₃){η⁵-1,2-[Co₂(CO)₆]-3,4-(Me₃SiO)₂-5-(Me₃Si)P₂C₃}Fe] ( 11 ). Constitution and configuration of compounds 1 c, 2 c, 8 – 11 were determined by elemental analyses and spectra (IR, ¹H-, ¹³C-, ³¹P-NMR, MS). In addition the molecular structure of 11 was established by single crystal X-ray analysis.     

Basische metalle : IX. Synthese und kristallstruktur von C5H5Co(PMe3)CS2. Reaktionen zu zweikernkomplexen mit Co(SCS)Cr- und Co(SCS)Mn-Brückenbindungen

C₅H₅Co(PMe₃)CS₂ (IV) is formed in practically quantitative yield in the reaction of C₅H₅Co(PMe₃)₂ (I) or the heterobinuclear complex C₅H₅(PMe₃)Co(CO)₂Mn(CO)C₅H₄Me (III) with CS₂. The crystal structure shows that the carbon disulfide bonds as a dihapto ligand through the carbon and one sulfur atom (S(2)) (CoC = 1.89, CoS(2) = 2.24 Å, S(2)CS(1) = 141.2°). The two CS bond lengths in IV (CS(2) = 1.68, CS(1) =1.60 Å) are greater than in free CS₂ (1.554Å) which is in agreement with the strong π-acceptor character of h²-CS₂ as shown in the spectroscopic data. IV reacts with Cr(CO)₅THF and C₅H₅Mn(CO)₂THF to give the complexes C₅H₅(PMe₃)Co(SCS)Cr(CO)₅ (V) and C₅H₅(PMe₃)Co(SCS)Mn(CO)₂C₅H₅ (VI) respectively, in which the sulfur atom S(1) that is not bound to cobalt coordinates to the 16-electron fragments Cr(CO)₅ and Mn(CO)₂C₅H₅. The spectroscopic data of IV, V and VI are discussed.     

Übergangsmetall-komplexe mit schwefelliganden: III. Eisen(II)-komplexe mit dem neuen fünfzähnigen thiol-thioether-liganden dpttd-H2 = 2,3,11,12-dibenzo-1,4,7,10,13-pentathia tridecan,synthese und reaktionen von komplexen des typs [Fe(dpttd)L], L = CO,PR3, DMSO,DMF, N2H4

Alkylation of [Fe(S₂C₆H₄)₂(CO)₂]^2? with S(C₂H₄Br)₂ yields loosing one CO ligand the monocarbonyl complex [Fe(dpttd)CO], where dpttd represents the dianion of the novel pentadentate thioether-thiol ligand dpttd-H₂ = 2,3,11,12-dibenzo-1,4,7,10,13-pentathiatridecan. The extremely stable [Fe(dpttd)CO] forms several coordination isomers with different ν(CO) frequencies. Dependent on the reaction conditions, the thermal or photochemical reaction of [Fe(dpttd)CO] with N₂H₅OH yields [Fe(dpttd)(N₂H₄)_2–3] or [Fe(dpttd)(N₂H₄)]·THF; the latter can also be obtained from [Fe(dpttd){P(OPh)₃}] and N₂H₄ in THF at 5–10°C. The CO ligand of [Fe(dpttd)CO] can be substituted thermally by PMe₃, PEt₃, PMePh₂ or P(OPh)₃ yielding the corresponding phosphine and phosphite complexes, but CO substitution by PPh₃ does not take place. Dissolution of [Fe(dpttd)(N₂H₄)_2–3] in dimethyl sulfoxide (DMSO) leads to [Fe(dpptd)(DMSO)], which yields [Fe(dpttd)(DMF)] at 80°C in dimethyl formamide (DMF). [Fe(dpttd)CO] is stable to air in the solid state as well as in solution, however, it decomposes on oxidation by H₂O₂, I₂, Br₂ or N-bromosuccinimide loosing CO and with destruction of the sulfur ligand. All complexes are not very soluble or hardly soluble in all common solvents; this is also found for methyl-substituted [Fe(dpttd)CO], which is obtained from [Fe(S₂C₆Me₄)₂(CO)₂]^2? and S(C₂H₄Br)₂. Oxidation or thermal decomposition of the N₂H₄ complexes yields [Fe(dpttd)]_x, from which [Fe(dpttd)CO] regenerates rapidly on treatment with CO.