Übergangsmetall-substituierte Acylphosphane und Phosphaalkene. 22 [1] Insertionen von Hexafluoraceton in die PX-Bindung von Metallophosphanen des Typs (η5-C5Me5)(CO)2M?PX2 (M = Fe,Ru; X = Me3Si,Cl). Strukturbestimmung von (η5-C5Me5)(CO)2Fe?P(SiMe3)C(CF3)2(OSiMe3)

Transition Metal-substituted Acylphosphanes and Phosphaalkenes. 22. Insertions of Hexafluoroacetone into the PX-Bond of Metallophosphanes (η⁵-C₅Me₅)(CO)₂M? PX₂ (M = Fe, Ru; X = Me₃Si, Cl). Structure Determination of (η⁵-C₅Me₅)(CO)₂Fe? P(SiMe₃)C(CF₃)₂(OSiMe₃) Reaction of the metallophosphanes (η⁵-C₅Me₅)(CO)₂M? P(SiMe₃)₂ ( 1a : M = Fe; 1b : M = Ru) with hexafluoroacetone (HFA) afforded the complexes (η⁵-C₅Me₅)(CO)₂M? P(SiMe₃)C(CF₃)₂(OSiMe₃) ( 2a, b ). The attempted synthesis of a metallophosphaalkene from 2a by thermal elimination of hexamethyldisiloxane failed. The acid catalyzed hydrolysis of 2a afforded compound (η⁵-C₅Me₅) · (CO)₂Fe? P(H)C(CF₃)₂(OSiMe₃) ( 3 ). Hexafluoracetone and (η⁵-C₅Me₅)(CO)₂Fe? PCl₂ ( 4 ) under-went reaction to give the metallochlorophosphan (η⁵-C₅Me₅) · (CO)₂Fe? P(Cl)? O? C(CF₃)₂Cl ( 5 ). Constitutions and configurations of the compounds ( 2–5 ) were established by elemental analyses and spectroscopic data (IR, ¹H-, ¹³C, ¹⁹F-, ²⁹Si-, ³¹P-NMR, MS). The molecular structure of 2a was determined by x-ray diffraction analysis.     

Structure of ansa-dimethylsilyl-bis(η5-cyclopentadienyl)titana(IV) cyclohexasulfane,Ti[Me2Si(η5-C5H4)2]S5

The X-ray crystal structure of Ti[Me₂Si(η⁵-C₅H₄)₂]S₅ has been determined. The coordination about the titanium may be described as a distorted tetrahedron. The (centroid)? Ti? (centroid) angle is 129.2° and the S? Ti? S bond angle 96.1°. The cyclopentadienyl rings are linked by a dimethylsilyl bridge. The sixmembered ring TiS₅ has a cyclohexane-like chair configuration. The four S? S distances range from 2.048 to 2.059 Å. Important structural dimensions are compared to those of similar type compounds.     

Ein Beitrag zur Reaktivität von (η5-C5Me5)(CO)2FeP(SiMe3)2 gegenüber P-Chlormethylenphosphanen

On the Reactivity of (η⁵-C₅Me₅)(CO)₂FeP(SiMe₃)₂ Toward P-Chloromethylene phosphanes The reaction of (η⁵-C₅Me₅)(CO)₂FeP(SiMe₃)₂ ( 2 ) with three equivalents of Cl? P?C(SiMe₃)₂ ( 3a ) afforded the 3-methanediyl-1,3,5,6-tetraphosphabicyclo[3.1.0]hex-2-ene (η⁵-C₅Me₅)(CO)₂Fe? ( 6a ). In contrast, 2 reacts with two equivalents of Cl? P?C(Ph)SiMe₃ ( 3b ) to give the thermolabile (η⁵-C₅Me₅) · (CO)₂Fe? P[P?C(Ph)SiMe₃]₂ ( 4b ) which decomposed during the reaction with further 3b. 4 b was also obtained from (η⁵-C₅Me₅)(CO)₂Fe? P(SiMe₃)? P?C(SiMe₃)₂ ( 1a ) and two equivalents of 3b .     

Heterometallische Clusterkomplexe der Typen Re2(μ-PR2)(CO)8(HgY) und ReMo(μ-PR2)(η5-C5H5)(CO)6(HgY) (R = Ph,Cy; Y = Cl,W(η5-C5H5)(CO)3)

Heterometallic Cluster Complexes of the Types Re₂(μ-PR₂)(CO)₈(HgY) and ReMo(μ-PR₂)(η⁵-C₅H₅)(CO)₆(HgY) (R = Ph, Cy; Y = Cl, W(η⁵-C₅H₅)(CO)₃) Dinuclear complexes Re₂(μ-H)(μ-PR₂)(CO)₈ and ReMo(μ-H)(μ-PR₂)(η⁵-C₅H₅)(CO)₆ (R = phenyl, cyclohexyl) were deprotonated and reacted as anions with HgCl₂ to compounds of the both types Re₂(μ-PR₂)(CO)₈HgCl) and ReMo(μ-PR₂)(η⁵-C₅H₅)(CO)₆(HgCl). The heterometallic three-membered cluster complexes correspond to an isolobal exchange of a proton against a cationic HgCl⁺ group. For one of the products ReMo(μ-PCy₂)(η⁵-C₅H₅)(CO)₆(HgCl) has been shown its conversion with NaW(η⁵-C₅H₅)(CO)₃ to ReMo(μ-PCy₂)(η⁵-C₅H₅)(HgW(η⁵-C₅H₅)(CO)₃) under substitution of the chloro ligand, par example. The newly prepared compounds were characterized by means of IR, UV/VIS and ³¹P NMR data. A complete determination of the molecular structure by single crystal analyses was done in the case of Re₂(μ-PCy₂)(CO)₈(HgCl) and of ReMo(μ-PCy₂)(η⁵-C₅H₅)(CO)₆(HgCl) which both are dimer because of the presence of an asymmetric dichloro bridge, and of ReMo(μ-PCy₂)(η⁵-C₅H₅)(CO)₆(HgW(η⁵-C₅H₅)(CO)₃). The structural study illustrates through comparison the influence of various metal types on an interaction between centric and edge-bridged frontier orbitals in three-membered metal rings.