Die Molekül- und Kristallstrukturen von (CO)4 W(μ-S-t-C4H9)2W(CO)4, η7-C7H7W(μ-SC6H4CH3)3W(CO)3 und η7-C7H7W(μ-S-n-C4H9)3W(CO)(μ-S-n-C4H9)2W(CO)4

Molecular and Crystal Structures of (CO)₄W(μ-S-t-C₄H₉)₂W(CO)₄, η⁷-C₇H₇W(μ-SC₆H₄CH₃)₃W(CO)₃ and η⁷-C₇H₇W(μ-S-n-C₄H₉)₃W(CO)(μ-S-n-C₄H₉)₂W(CO)₄ The molecular structures of the two binuclear complexes (CO)₄W(μ-S-t-C₄H₉)₂W(CO)₄ and η⁷-C₇H₇W(μ-SC₆H₄CH₃)₃W(CO)₃ and of the tungsten cluster η⁷-C₇H₇W(μ-S-n-C₄H₉)₃W(CO)-(μ-S-n-C₄H₉)₂W(CO)₄ respectively are described. In the nonlinear trinuclear cluster the central tungsten atom is connected to the two tungsten atoms by two and three μ-S-n-C₄H₉ bridges respectively and additionally by one W? W bond each. The coordination sphere of the W atoms is completed by a η⁷-C₇H₇ ring and four CO groups respectively; the central tungsten carries an additional CO group.     

Beiträge zur Chemie des Phosphors. 227. HP4º als Komplexligand: Bildung und Eigenschaften von [(η5-C5H5)2ZrCl(P4H)], [(η5-C5Me5)2ZrCl(P4H)] und [(η5-C5H5)3Zr(P4H)]

Contributions to the Chemistry of Phosphorus. 227. HP₄º as a Complex Ligand: Formation and Properties of [(η⁵-C₅H₅)₂ZrCl(P₄H)], [(η⁵-C₅Me₅)₂ZrCl(P₄H)], and [(η⁵-C₅H₅)₃Zr(P₄H)] The novel complexes [(η⁵-C₅H₅)₂ZrCl(P₄H)] ( 1 ), [(η⁵-C₅Me₅)₂ZrCl(P₄H)] ( 2 ), and [(η⁵-C₅H₅)₃Zr(P₄H)] ( 3 ) have been obtained by reaction of a solution of (Na/K)HP₄ with the zirconocen derivatives [(η⁵-C₅H₅)₂ZrCl₂], [(η⁵-C₅Me₅)₂ZrCl₂], and [(η⁵-C₅H₅)₃(η¹-C₅ H₅)Zr] under suitable conditions. The structure of the compounds 1 – 3 , which are only stable in solution, has been elucidated by means of ³¹P-NMR spectroscopy. It is highly probable that the exo,endo isomer exists in each case. In addition, further isomers of lower relative abundancies have been observed, in which the ligands presumably exhibit a different spatial orientation relatively to each other.     

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.     

Zur Kenntnis der Chemie der Metallcarbonyle und der Cyanokomplexe in flüssigem Ammoniak. XXXII. Über die Reaktionen von η5-C5H5Mo(CO)3CH3 und η5-C5H5Fe(CO)2CH3 mit flüssigem Ammoniak

The Chemistry of Metal Carbonyls and Cyano Complexes in Liquid Ammonia. XXXII. On the Reaction of η⁵-C₅H₅Mo(CO)₃CH₃ and η⁵-C₅H₅Fe(CO)₂CH₃ with Liquid Ammonia η⁵-C₅H₅Mo(CO)₃CH₃ reacts with liquid NH₃ to give η⁵-C₅H₅Mo(CO)₂(NH₃)H and acetamide: In contrast, η⁵-C₅H₅Fe(CO)₂CH₃ undergoes a carbonyl insertion to give the acetyl complex η⁵-C₅H₅Fe(CO)(NH₃)COCH₃: The NH₃ ligand in η⁵-C₅H₅Fe(CO)(NH₃)COCH₃ can be substituted by pyridine.     

Phosphido- und arsenido-verbrückte Zweikernkomplexe: Synthese und Struktur von (η5-C5H4R)2Zr{μ-P(SiMe3)2}2M(CO)4 (R = Me,M = Cr; R = H,M = Mo) sowie die Synthese von (η5-C5H5)2Zr{μ-As(SiMe3)2}2Cr(CO)4

Phosphido- and Arsenido-bridged Dinuclear Complexes. Synthesis and Molecular Structure of (η⁵-C₅H₄R)₂Zr{μ-P(SiMe₃)₂}₂M(CO)₄ (R = Me, M = Cr; R = H, M = Mo) and Synthesis of (η⁵-C₅H₅)₂Zr{μ-As(SiMe₃)₂}₂Cr(CO)₄ The reaction of (η⁵-C₅H₄R)₂Zr{E(SiMe₃)₂}₂ with M(CO)₄(NBD) (NBD = norbornadiene) yields the dinuclear phosphido- or arsenido-bridged complexes (η⁵-C₅H₄R)₂Zr{μ-E(SiMe₃)₂}₂M(CO)₄ (R = Me, E = P, M = Cr ( 1 ); R = H, E = P, M = Mo ( 2 ); R = H, E = As, M = Cr ( 3 )). No formation of dinuclear complexes was observed in the reaction of (η⁵-C₅H₄Me)₂Zr{P(SiMe₃)₂}₂ with Ni(PEt₃)₄, Ni(CO)₂(PPh₃)₂ or with NiCl₂(PPh₃)₂ in the presence of Mg. Complexes 1 – 3 were characterised spectroscopically (i. r., n. m. r., m. s.), and X-ray structure investigations were carried out on 1 and 2 . The central four-membered ZrP₂M ring is slightly puckered (dihedral angle between planes ZrP₂/CrP₂ 14.7°, ZrP₂/MoP₂ 14.2°). The Zr? P bond lengths are equivalent ( 1 : Zr? P1 2.654(4), Zr? P2 2.657(4) Å; 2 : Zr? P1 2.6711(9), Zr? P2 2.6585(7) Å), as are the M? P bond lengths (M = Cr ( 1 ): Cr? P1 2.513(4), Cr? P2 2.502(4) Å; M = Mo ( 2 ): Mo? P1 2.6263(7), Mo? P2 2.6311(10) Å). The long Zr ··· M distances of 3.414 Å (M = Cr ( 1 )) and 3.461 Å (M = Mo ( 2 )) indicate the absence of a metal-metal bond.