Synthesen und Kristallstrukturen von [(t-Bu4Sb4)Fe(CO)4], [(t-Bu4Sb4)Mo(CO)5] und [(t-Bu3Sb4)Mo(η5-C5Me5)(CO)3]

Syntheses and Crystal Structures of [( t -Bu₄Sb₄)Fe(CO)₄], [( t -Bu₄Sb₄)Mo(CO)₅], and [( t -Bu₃Sb₄)Mo(η⁵-C₅Me₅)(CO)₃] t-Bu₄Sb₄ reacts with Fe₂(CO)₉ to form [(t-Bu₄Sb₄)Fe(CO)₄] ( 1 ). [(t-Bu₄Sb₄)Mo(CO)₅] ( 2 ) is formed from (thf)Mo(CO)₅ and t-Bu₄Sb₄. [(t-Bu₃Sb₄)Mo(η⁵-C₅Me₅)(CO)₃] ( 3 ) is a product of the reaction of t-Bu₄Sb₄ with [(η⁵-C₅Me₅)Mo(CO)₃]₂. The crystal structures of 1–3 are reported.     

Synthesis,Structure, and Redox Properties of [{(η5-C5H5)Co(S2C6H4)}2Mo(CO)2], a Novel Metalladithiolene Cluster

Metal–metal bond formation by a cobaltadithiolene complex was observed for the first time in the reaction of [Co(η⁵-C₅H₅)(S₂C₆H₄)] with [Mo(CO)₃(py)₃] and BF₃ to give the Co-Mo-Co cluster 1 . Cyclic voltammetry reveals that 1 undergoes two one-electron reduction steps at the Co centers, which is indicative of transmission of the Co−Co electronic interaction through the Mo center.     

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.     

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.