Metallkomplexe mit anionischen Liganden von Elementen der 4. Hauptgruppe. VIII. Pentacarbonyl-trihalogenstannido-metallat(O)-Komplexe von chrom,molybdän und wolfram mit fluor- und jodhaltigen stannidliganden

Metal Complexes with Anionic Ligands of Elements of the Main Group IV. VIII Pentacarbonyltrihalogenostannidometalate(O) Complexes of Chromium, Molybdenum, and Tungsten with Fluorine and Iodine Containing Trihalogenostannido Ligands In methylenechloride [As(C₆H₅)₄][SnF₃] readily reacts with the metalhexacarbonyls forming the arsoniumsalts of the pentacarbonyltrifluorostannidometalate(O) complexes, [M(CO)₅SnF₃]^? (M ? Cr, Mo, W). Exclusively by the reaction of the intermediately formed complex Cr(CO)₅THF only one pure triiodostannidometalate(O) Complex, [N(C₂H₅)₄][Cr(CO)₅SnJ₃], could be isolated. The trihalogenostannidometalate(O) complexes [M(CO)₅SnClX₂]^? (X ? F: M ? Cr, Mo, W; X ? J: M ? Cr) could be prepared by SnX₂-insertion reactions of the [M(CO)₅Cl]^? complexes. The bonding properties of the halogenostannide ions are discussed on the bases of the IR spectra of their metalate(O) complexes.     

Diimido‐, Imido(oxo)‐, Dioxo‐ und Imido(alkyliden)‐Halbsandwich‐Verbindungen über selektive Hydrolyse und α—H‐Abstraktion an Organylkomplexen des sechswertigen Molybdäns und Wolframs

Diimido, Imido Oxo, Dioxo, and Imido Alkylidene Halfsandwich Compounds via Selective Hydrolysis and α—H Abstraction in Molybdenum(VI) and Tungsten(VI) Organyl Complexes Organometal imides [(η⁵‐C₅R₅)M(NR′)₂Ph] (M = Mo, W, R = H, Me, R′ = Mes, tBu) 4 — 8 can be prepared by reaction of halfsandwich complexes [(η⁵‐C₅R₅)M(NR′)₂Cl] with phenyl lithium in good yields. Starting from phenyl complexes 4 — 8 as well as from previously described methyl compounds [(η⁵‐C₅Me₅)M(NtBu)₂Me] (M = Mo, W), reactions with aqueous HCl lead to imido(oxo) methyl and phenyl complexes [(η⁵‐C₅Me₅)M(NtBu)(O)(R)] M = Mo, R = Me ( 9 ), Ph ( 10 ); M = W, R = Ph ( 11 ) and dioxo complexes [(η⁵‐C₅Me₅)M(O)₂(CH₃)] M = Mo ( 12 ), M = W ( 13 ). Hydrolysis of organometal imides with conservation of M‐C σ and π bonds is in fact an attractive synthetic alternative for the synthesis of organometal oxides with respect to known strategies based on the oxidative decarbonylation of low valent alkyl CO and NO complexes. In a similar manner, protolysis of [(η⁵‐C₅H₅)W(NtBu)₂(CH₃)] and [(η⁵‐C₅Me₅)Mo(NtBu)₂(CH₃)] by HCl gas leads to [(η⁵‐C₅H₅)W(NtBu)Cl₂(CH₃)] 14 und [(η⁵‐C₅Me₅)Mo(NtBu)Cl₂(CH₃)] 15 with conservation of the M‐C bonds. The inert character of the relatively non‐polar M‐C σ bonds with respect to protolysis offers a strategy for the synthesis of methyl chloro complexes not accessible by partial methylation of [(η⁵‐C₅R₅)M(NR′)Cl₃] with MeLi. As pure substances only trimethyl compounds [(η⁵‐C₅R₅)M(NtBu)(CH₃)₃] 16 ‐ 18 , M = Mo, W, R = H, Me, are isolated. Imido(benzylidene) complexes [(η⁵‐C₅Me₅)M(NtBu)(CHPh)(CH₂Ph)] M = Mo ( 19 ), W ( 20 ) are generated by alkylation of [(η⁵‐C₅Me₅)M(NtBu)Cl₃] with PhCH₂MgCl via α‐H abstraction. Based on nmr data a trend of decreasing donor capability of the ligands [NtBu]^2— > [O]^2— > [CHR]^2— ? 2 [CH₃]^— > 2 [Cl]^— emerges.     

Metallkomplexe mit 1,2-Dithion-Liganden. III. Dithiooxamide als starke Donatoren oder Akzeptoren in Molybdäncarbonylkomplexen

Metal Complexes with 1,2-Dithione Ligands. III. Dithiooxamides as Strong Donors or Acceptors in Molybdenum Carbonyl Complexes. Starting from substitution labile molybdenum carbonyl complexes L₂Mo(CO)₄, L₃Mo(CO)₃ and L₂L₂′Mo(CO)₂ several new complex types with the C? C-twisted tetraalkyldithiooxamides (R₄dto) and the planar N,N′-dialkyldithiooxamides (R₂H₂dto) such as (R₄dto)Mo(CO)₄ ( 8 – 11 ), (R₂H₂dto)Mo(CO)₄ ( 12 – 18 ), (R₂R₂′dto)Mo(CO)₃(P(C₆H₅)₃) ( 27 – 31 ), (R₂R₂′dto)Mo(CO)₂(PR₃)₂ ( 36 – 51 ) are described and compared with complexes of a cyclic dithiooxamide ( 62 – 64 ) and analogous complexes with thioamides R₂NC(S)R′ ( 19 – 25 , 52 – 55 , 57 – 60 ). In Mo(CO)₄ complexes, dithiooxamides display a rather strong donor character and are thus similar to simple thioamides, but the blue colour of the R₂H₂dto complexes indicates already low-lying acceptor levels. When passing from the Mo(CO)₄ complexes via Mo(CO)₃(PR₃) complexes to the very electron rich Mo(CO)₂(PR₃)₂ complexes, the i.r. and eletronic spectra indicate an unexpected and drastic change in ligand character. Dto ligands in the latter complex type turn out to be very strong acceptors, independent of the degree of N-alkylation. A conformational change, with twisted R₂N? C bonds and a planar S? C? C? S skeleton (as in the dithiolene complexes), can account for all the peculiarities of the (dto)-dicarbonylbis(phosphine) complexes as compared to the “normal” thioamide complexes. Dithiooxamides can thus control the oxidation state of metals by a remote conformational change and possibly act as an electron reservoir in chemical reactions at the metal center.     

Schwefeldioxid als Ligand und Synthon. XII. Synthese und Reaktivität von Nickel(II)-Komplexen dreizähniger anionischer Liganden des Typs (C6H3{CH2NR1R2}2-2,6)−

Sulfur Dioxide as Ligand and Synthon. XII. Synthesis and Reaction Behaviour of Nickel(II) Complexes with Terdendate Anionic Ligands of the Type (C₆H₃{CH₂NR¹R²}₂?2,6)^? Organonickel(II) complexes of the type [NiX{C₆H₃(CH₂NR¹R²)₂?2,6}] (X = halide OH₂⁺/CF₃SO₃^?; R¹?R²?Et 1 ; R¹?R²?i? Pr 2 ; R¹ = Me, R² = Cy 3 ; (NR¹R²) = piperidino 4 ; (NR¹R²) = pyrrolidino 5 ) are described. ¹H and ¹³C NMR and UV/Vis spectra were recorded, and the X-ray crystal structure of 1 a (X = Br) was determined. This complex crystallizes orthorhombically in the space group Pbca with a = 1 335.8(2) pm, b = 1 903.3(3) pm, c = 1 365.4(3) pm and Z = 8, and has an approximately square-planar geometry. 4 and 5 show a reversible binding of SO₂ which has been detected by means of IR photoacoustic spectroscopy. The reactions of 1 – 5 with CS₂ and PhNSO are discussed.     

Perfluormethyl-Element-Liganden. XXXV. Reaktivität metallierter Phosphane und Arsane des Typs π-C5H5(CO)3MER2 (M  Cr,Mo, W; E  P,As; R  CF3, CN)

Perfluoromethyl-Element-Ligands. XXXV. Reactivity of Metallated Phosphanes and Arsanes of the Type π-C₅H₅(CO)₃MER₂ (M ? Cr, Mo, W; E ? P, As; R ? CF₃, CN) The influence of the complex fragments π-C₅H₅(CO)₃M (M ? Cr, Mo, W) on the basicity of the metallated phosphanes or arsanes π-C₅H₅(CO)₃MER₂ (E ? P, As; R ? CF₃, CN) has been investigated by reactions with sulfur, methyliodide, fluorotrichloromethane, and W(CO)₅THF, respectively. π-C₅H₅(CO)₃ME(CF₃)₂ (E ? P: 1a–c ; E ? As: 2a–c ) react with sulfur only for E ? P to give the complexes π-C₅H₅(CO)₃P(S)(CF₃)₂ ( 5a–c ) in good yield. The attempted thermal transformation of the phosphane sulfides to η² coordinated (CF₃)₂P?S complexes proves unsuccessful. The reactions of 1a–c, 2a–c and π-C₅H₅(CO)₃MP(CN)₂ ( 3a–c ) with CH₃I or CCl₃F do not lead to onium salts, but to cleavage of the M–E bonds forming π-C₅H₅(CO)₃MX (X ? I, Cl) and CH₃ER₂ and R₂ECCl₂F, respectively. The reactivity depends on ER₂ and M: P(CF₃)₂ > P(CN)₂ > As(CF₃)₂; Cr > Mo > W. Due to the low donor ability of the complexes 1a–c, 2a–c and 3a–c binuclear compounds π-C₅H₅(CO)₃MER₂W(CO)₅ (E ? As, R ? CF₃: 11a–c ; E ? P, R ? CN: 12a–c ; ER₂?P(CN)Ph: 13a, b ) are obtained only with the highly reactive W(CO)₅THF. In case of the (CF₃)₂P bridged derivatives spontaneous CO-elimination leads to the threemembered ring systems ( 10a–c ).     

Synthese und spektroskopische Charakterisierung einiger Pentacarbonylwolfram(0)-Komplexe mit verschiedenen 1H-Phosphiren-Liganden,Kristallstrukturen von,und

Synthesis and Spectroscopic Characterization of some Pentacarbonyltungsten(0) Complexes with Various 1H-Phosphirene Ligands: Crystal Structures of , and The tungsten(0) complex 1 reacts upon heating with acetylene derivatives 2a–f in toluene to form benzonitrile and the complexes 4a–f ( 4a : R¹ ? Ph, R² ? H; 4b : R¹ ? Ph, R² ? CH₃; 4c : R¹ ? OEt, R² ? H; 4d : R¹ ? Ph, R² ? CO₂Et; 4e : R¹, R² ? CO₂Me; 4f : R¹, R² ? SiMe₃), which have been isolated by chromatography. Spectroscopic and mass spectrometric data are discussed. The crystal structures of the compounds 4a, b and d were determined by X-ray single crystal structure analysis ( 4a : space group P2₁/n, Z = 4, a = 937,5(2) pm, b = 2202,4(6) pm, c = 1266,3(4) pm, β = 108,94(4)°; 4b : space group P2₁/c, Z = 4, a = 1293,9(2) pm, b = 923,5(1) pm, c = 2223,4(3) pm, β = 92,385(6)°; 4d : space group P2₁/c, Z = 4, a = 955,2(2) pm, b = 3190,9(4) pm, c = 930,7(2) pm, β = 99,64(1)°).     

Light‐Induced Rearrangement of Thioether‐Substituted Phosphanide Ligands: Scope and Limitations of a Remarkable Isomerization

Treatment of the thioether‐substituted secondary phosphanes R²PH(C₆H₄‐2‐SR¹) [R²=(Me₃Si)₂CH, R¹=Me ( 1_PH ), iPr ( 2_PH ), Ph ( 3_PH ); R²=tBu, R¹=Me ( 4_PH ); R²=Ph, R¹=Me ( 5_PH )] with nBuLi yields the corresponding lithium phosphanides, which were isolated as their THF ( 1 – 5_Pa ) and tmeda ( 1 – 5_Pb ) adducts. Solid‐state structures were obtained for the adducts [R²P(C₆H₄‐2‐SR¹)]Li(L)_n [R²=(Me₃Si)₂CH, R¹=nPr, (L)_n=tmeda ( 2_Pb ); R²=(Me₃Si)₂CH, R¹=Ph, (L)_n=tmeda ( 3_Pb ); R²=Ph, R¹=Me, (L)_n=(THF)_1.33 ( 5_Pa ); R²=Ph, R¹=Me, (L)_n=([12]crown‐4)₂ ( 5_Pc )]. Treatment of 1_PH with either PhCH₂Na or PhCH₂K yields the heavier alkali metal complexes [{(Me₃Si)₂CH}P(C₆H₄‐2‐SMe)]M(THF)_n [M=Na ( 1_Pd ), K ( 1_Pe )]. With the exception of 2_Pa and 2_Pb , photolysis of these complexes with white light proceeds rapidly to give the thiolate species [R²P(R¹)(C₆H₄‐2‐S)]M(L)_n [M=Li, L=THF ( 1_Sa , 3_Sa – 5_Sa ); M=Li, L=tmeda ( 1_Sb , 3_Sb – 5_Sb ); M=Na, L=THF ( 1_Sd ); M=K, L=THF ( 1_Se )] as the sole products. The compounds 3_Sa and 4_Sa may be desolvated to give the cyclic oligomers [[{(Me₃Si)₂CH}P(Ph)(C₆H₄‐2‐S)]Li]₆ (( 3_S )₆) and [[tBuP(Me)(C₆H₄‐2‐S)]Li]₈ (( 4_S )₈), respectively. A mechanistic study reveals that the phosphanide–thiolate rearrangement proceeds by intramolecular nucleophilic attack of the phosphanide center at the carbon atom of the substituent at sulfur. For 2_Pa / 2_Pb , competing intramolecular β‐deprotonation of the n‐propyl substituent results in the elimination of propene and the formation of the phosphanide–thiolate dianion [{(Me₃Si)₂CH}P(C₆H₄‐2‐S)]^2?.     

Komplexe des Chroms,Molybdäns und Wolframs mit Aminoarsan-Liganden

Complexes of Chromium, Molybdenum, and Tungsten with Aminoarsanes as Ligands The aminoarsanes Me₂As? NMe₂, MeAs(NMe₂)₂, and As(NMe₂)₃ form with the carbonyles of the sub-group VI metals complexes of the general formula (CO)₅M? L (L = aminoarsane; M ? Cr, Mo, W). The cleavage of the As? N bond by reactions with acids HX results in the formation of complexes of the general formula (CO)₅M? As(Me₂)? X, (CO)₅M? As(Me)X₂, and (CO)₅M? AsX₃.     

Metallcarbonylkomplexe mit mehrzähnigen ringförmigen Liganden. I. Pentacarbonylkomplexe des s-Trithians und verwandter Verbindungen

Carbonyl Metal Compounds with Polydentate Cyclic Ligands. I. Pentacarbonyl Complexes of s-Trithiane and Related Compounds The complexes (RCHS)_nM(CO)₅ (R = H, CH₃, n = 3; R = H, n = 4; M = Cr^, Mo, W) were prepared from the tetrahydrofuran pentacarbonyl metal compounds and the respective ligands. The Cotton-Kraihanzel force constants of these complexes indicate the sulfur ligands to be slightly more basic than triphenylphosphine. The trimethyltrithiane complexes (R = CH₃, n = 3) exhibit rapid intramolecular exchange of the M(CO)₅-group along the three coordination centers of the ligand.     

Zur Reaktivität der Ferriophosphaalkene [(η5‐C5Me5)(CO)2FeP=C(NR)R2] (NR = NMe2, NC5H10, R2 = Ph,tBu) gegenüber Protonsäuren,Alkylierungsmitteln und [{(Z)‐Cycloocten}Cr(CO)5]

Transition Metal‐substituted Phosphaalkenes. 42 Reactivity of the Ferriophosphaalkenes [(η⁵‐C₅Me₅)(CO)₂FeP=C(NR )R²] (NR = NMe₂, NC₅H₁₀, R² = Ph, t Bu) towards Protic Acids, Alkylation Reagents, and [{( Z )‐Cyclooctene}Cr(CO)₅] The reaction of equimolar amounts of [(η⁵‐C₅Me₅)(CO)₂FeP=C(NR )R²] ( 2 a : NR = NMe₂, R² = Ph; 2 b : NMe₂. tBu; 2 c : NC₅H₁₀, Ph) and etherial HBF₄ gave rise to the formation of [(η⁵‐C₅Me₅)(CO)₂FeP(H)C(NR )R²] (BF₄) ( 3 a – c ) which were isolated as light red powders. Compounds 2 a – c were converted into [(η⁵‐C₅Me₅)(CO)₂FeP(Me)C(NR )R²] (SO₃CF₃) ( 4 a – c ) by treatment with methyl trifluoromethane sulfonate. In addition 2 a and Me₃SiCH₂OSO₂CF₃ afforded light red [(η⁵‐C₅Me₅)(CO)₂FeP(CH₂SiMe₃)C(NMe₂)Ph](SO₃CF₃) ( 5 ). The black complex [(η⁵‐C₅Me₅)(CO)₂FeP{Cr(CO)₅}C(NMe₂)Ph] ( 6 ) resulted from the combination of 2 a with [{(Z)‐cyclooctene}Cr(CO)₅]. The novel products were characterized by elemental analyses and spectra (IR, ¹H‐, ¹³C‐ und ³¹P‐NMR).     

Beiträge zur Komplexchemie der Phosphine und Phosphinoxide. XXXI. Cobalt- sowie Rhodiumkomplexe primärer Mercaptoalkylphosphine und Bemerkungen zur Komplexbildung quadridentater P,P,S,S-Liganden

On the Coordination Chemistry of Phosphines and Phosphinoxides. XXXI. Cobalt and Rhodium Complexes of Primary Mercaptoalkylphosphines and Remarks on the Complex Formation of Quadridentate P,P,S,S Ligands Primary Mercaptoalkylphosphines (H₂P? CH₂ · CH₂? SH; H₂P? CH₂ · CHCH₃? SH) react with d⁷-metal salts to give octahedron 1:3 chelat complexes. In case of cobalt the oxidation of Co^II to Co^III are obtained by formation of H₂. Structure and properties of these complexes as well as their reactivity like S-alkylation or metallation with following reactions are described. Reaction scheme see ?Inhaltsübersicht”?. With quadridentate ligands HS+ +PH+ +PH+ +SH = L result chelat-complexes of the type [M^III? L XNH₃] (M = Co, Rh) and such as [M^II? L] (M = Ni, Pd, Pt).     

Darstellung und stabilität von n,n-disubstituierten β-aminoethyl-magnesiumbromiden; die ersten β-heteroatomsubstituierten grignardverbindungen des typs R2NCH2CH2MgX

R₂NCH₂,CH₂BR (R₂ = Ph₂; Ph, Me; (C₆H₁₁)₂)reacts with highly activated magnesium between ?75 and ?100°c in THF and ether to give the Grignard compounds R₂NCH₂CH₂MgBr, which already decompose between ?90 and?20°c by elimination of ethylene. The thermal stability increases in the sequence R₂ = Ph, Me < Ph₂ < (C₆H₁₁).     

Perfluormethyl-Element-Liganden. XXXII. Reaktionen der Metallhydride π-C5H5(CO)3MH (M = Cr,Mo, W) mit Diphosphanen [Ph2−nYnP]2 (Y = I,CN, SiMe3; n = 2, 1, 0)

Perfluoromethyl Element Ligands. XXXII. Reactions of the Metal Hydrides π-C₅H₅(CO)₃MH (M = Cr, Mo, W) with Diphosphanes [Ph_2?nY_nP]₂ (Y = I, CN, SiMe₃; n = 2, 1, 0) The reactions of π-C₅H₅(CO)₃MH (M = Cr, Mo, W) ( 1a – c ) with the symmetric diphosphanes (Ph₂P)₂, [Ph(CN)P]₂, [(CN)₂P]₂, and the cyclophosphane (PPh)₅, respectively, occur under cleavage of the P? P bond. The reactivity decreases in the series The tendency to form binuclear complexes reflects the basicity of the metallated phosphanes π-C₅H₅(CO)₃MPRR′ and increases in the order P(CN)₂ < P(CN)Ph ? P(Ph)H < PPh₂. Iodine containing diphosphanes [Ph(I)P? P(I)Ph and P₂I₄] undergo redox reactions with 1a – c , yielding π-C₅H₅(CO)₃MI and unstable iodo-diphosphanes. No P? P bond cleavage occurs in the reaction of the silyl substituted diphosphanes [Ph(SiMe₃)P]₂ and [(Me₃Si)₂P]₂ with 1a – c , but P? Si bond fission is the preferred reaction giving π-C₅H₅(CO)₃MSiMe₃.     

Metallkomplexe mit biologisch wichtigen Liganden. CLVII [1] Halbsandwich‐Komplexe mit Isocyanoacetylaminosäureestern und Isocyanoacetyldi‐ und tripeptidestern („Isocyano‐Peptide”︁)

Metal Complexes of Biologically Important Ligands, CLVII [1] Halfsandwich Complexes of Isocyanoacetylamino acid esters and of Isocyanoacetyldi‐ and tripeptide esters (?Isocyanopeptides”?) N‐Isocyanoacetyl‐amino acid esters CNCH₂C(O) NHCH(R)CO₂CH₃ (R = CH₃, CH(CH₃)₂, CH₂CH(CH₃)₂, CH₂C₆H₅) and N‐isocyanoacetyl‐di‐ and tripeptide esters CNCH₂C(O)NHCH(R¹)C(O)NHCH(R²)CO₂C₂H₅ and CNCH₂C(O)NHCH(R¹)C(O)NHCH (R²)C(O)NHCH(R³)CO₂CH₃ (R¹ = R² = R³ = CH₂C₆H₅, R² = H, CH₂C₆H₅) are available by condensation of potassium isocyanoacetate with amino acid esters or peptide esters. These isocyanides form with chloro‐bridged complexes [(arene)M(Cl)(μ‐Cl)]₂ (arene = Cp*, p‐cymene, M = Ir, Rh, Ru) in the presence of Ag[BF₄] or Ag[CF₃SO₃] the cationic halfsandwich complexes [(arene)M(isocyanide)₃]⁺X^? (X = BF₄, CF₃SO₃).     

Alternativ-Liganden. III. Koordinatives verhalten von chelatliganden des typs me2XSi(Me2)CH2XMe2 (X  N und/oder P: Me  CH3)

Co-ordinative Properties of Chelating Ligands of the Type Me₂XSi(Me₂)CH₂XMe₂ (X ? N and/or P; Me ? CH₃) The reactions of the ligands L ? Me₂XSi(Me₂)CH₂XMe₂ (X ? N and/or P; Me ? CH₃) with M(CO)₆ and M(CO)₄norbor (norbor ? norbornadiene) (M ? Cr, Mo), respectively, yield derivatives of the types M(CO)₅L, M(CO)₄L, and M(CO)₄L₂, respectively. M(CO)₅L compounds are formed from the hexacarbonyls with Me₂NSiMe₂CH₂PMe₂, whereas the ligand Me₂NSiMe₂CH₂NMe₂ does not afford analogous derivatives under the same conditions. Even on substitution of the diene-ligand in M(CO)₄norbor by Me₂NSiMe₂CH₂PMe₂ the chelate complexes M(CO)₄NMe₂SiMe₂CH₂PMe₂ are not obtained, but the cis-disubstituted products M(CO)₄[PMe₂CH₂SiMe₂NMe₂]₂ with phosphorus acting as donor atom are produced. The ligands Me₂PSiMe₂CH₂XMe₂(X ? N, P) give the chelate complexes M(CO)₄PMe₂SiMe₂CH₂XMe₂ in high yields. The new compounds were identified by analytical and spectroscopic (PMR, IR, mass spectra) methods.     

Übergangsmetallphosphido-Komplexe. XIV. P-funktionelle phosphidoverbrückte Heterozweikern-komplexe mit und ohne Metall- Metall-Bindung; PH2-verbrückte cp(CO)xFe-Derivate

Transition Metal Phosphido Complexes. XIV. P-Functional Phosphido-Bridged Heterobimetallic Complexes with and without a Metal-Metal Bond; PH₂-Bridged cp(CO)_xFe-Derivatives Cleaving both Si? P bonds in the complexes cp(CO)₂[μ-P(SiMe₃)₂]M′L_m 1 (M′L_m = Co(CO)₂(NO) b , Fe(CO)(NO)₂ c Mn(NO)₃ d , Cr(CO)₅ f , Mo(CO)₅ g , W(CO)₅ h , Mncp(CO)₂ i , MnMecp(CO)₂ j , Crcp(CO)(NO) k , Vcp(CO)₃ l ) using CH₃OH, H₂O or CH₃COOH, respectively, gives the PH₂-bridged bimetallic complexes cp(CO)₂Fe(μ-PH₂)M′L_m 2b – d and 2f – l . The complexes H₃PM′L_m 4e, 4f, 4j (M′L_m = Fe(CO)₄ e ) which can be obtained reacting the P-silylated derivatives (Me₃Si)₃PM′L_m with CH₃OH can be transformed into LiH₂PM′L_m 5e, 5f, 5j using n-BuLi. 5e, 5f, 5j react with cp(CO)₂ FeBr to give 2e, 2f, 2j . The photochemical decarbonylation of 2b - l leads only in the case of 2i and 2j to isolable complexes containing a metal-metal bond cp(CO)Fe(μ-CO, μ-PH₂) M′L_m?1 6 (M′L_m?1 = Mncp(CO) i , MnMecp(CO) j ). 6i and 6j as well as 6k (M′L_m?1 = Crcp(NO) k ) are also available cleaving both Si? P bonds in cp(CO)Fe[μ-CO, μ-P(SiMe₃)₂]M′L_m?1 8i – k using CH₃OH. In other complexes 6 the PH₂-bridge causes a labilisation of the metal-metal bond. This can be used in some cases to add ligands under mild conditions. I.R., N.M.R. and mass spectral data are reported.     

Über die Natur der Übergangsmetall-Kohlenstoff-σ-Bindung. V. Darstellung und Reaktivität von N,N-disubstituierten β-Amino-ethyleisen(II)-phthalocyaninkomplexen Na[PcFeCH2CH2NR2] · x THF

On the Nature of the Transition Metal Carbon-σ-Bond. V. Preparation and Reactivity of N,N-disubstituted β-Aminoethyl Iron (II) Phthalocyanines Na[PcFeCH₂CH₂NR₂] · x THF β-Aminoethyl halides react with iron(0) phthalocyanine in an oxidative addition reaction to form olive-green diamagnetic complexes Na[PcFeCH₂CH₂NR₂] · x THF (R₂ = Ph₂, x = 4; R₂ = Ph, Me, x = 3; R₂ = (CH₂)₅, x = 5), which in turn react with p-toluenesulfonic acid, methanol, acetyl chloride and methyl iodide in a heterolytic fragmentation reaction to give FePc, CH₂?CH₂ as well as R₂NH, MeC(O)NR₂ and [R₂NMe₂]I, respectively. On reduction with LiAlH₄ the phenylmethylaminoethyl complex undergoes a fragmentation reaction, too, and catalyses the trimerisation of phenyl isocyanate to (PhNCO)₃.     

Gemischte Sandwichkomplexe der 4 f‐Elemente: Enantiomerenreine Cyclooctatetraenyl‐Cyclopentadienyl‐Komplexe des Samariums und Lutetiums mit donorfunktionalisierten Cyclopentadienylliganden

Organometallic Compounds of the Lanthanides. 139 Mixed Sandwich Complexes of the 4 f Elements: Enantiomerically Pure Cyclooctatetraenyl Cyclopentadienyl Complexes of Samarium and Lutetium with Donor‐Functionalized Cyclopentadienyl Ligands The reactions of [K{(S)‐C₅H₄CH₂CH(Me)OMe}], [K{(S)‐C₅H₄CH₂CH(Me)NMe₂}] and [K{(S)‐C₅H₄CH(Ph)CH₂NMe₂}] with the cyclooctatetraenyl lanthanide chlorides [(η⁸‐C₈H₈)Ln(μ‐Cl)(THF)]₂ (Ln = Sm, Lu) yield the mixed cyclooctatetraenyl cyclopentadienyl lanthanide complexes [(η⁸‐C₈H₈)Sm{(S)‐η⁵ : η¹‐C₅H₄CH₂CH(Me)OMe}] ( 1 a ), [(η⁸‐C₈H₈)Ln{(S)‐η⁵ : η¹‐C₅H₄CH₂CH(Me)NMe₂}] (Ln = Sm ( 2 a ), Lu ( 2 b )) and [(η⁸‐C₈H₈)Ln{(S)‐η⁵ : η¹‐C₅H₄CH(Ph)CH₂NMe₂}] (Ln = Sm ( 3 a ), Lu ( 3 b )). For comparison, the achiral compounds [(η⁸‐C₈H₈)Ln{η⁵ : η¹‐C₅H₄CH₂CH₂NMe₂}] (Ln = Sm ( 4 a ), Lu ( 4 b )) are synthesized in an analogous manner. ¹H‐, ¹³C‐NMR‐, and mass spectra of all new compounds as well as the X‐ray crystal structures of 3 b and 4 b are discussed.