Übergangsmetallkomplexe der Liganden PhAsH₂ und Ph₂As₂H₂; Struktur und Epimerisierung von meso‐Ph₂As₂H₂[Mn(CO)₂C₅H₅]₂

Abstract

Phenylarsine. PhAsH,, reacts with the tetrahydrofuran adducts (CO),M(THF) (M = Cr, Mo, W) to give the corresponding pentacarbonylmetal complexes (CO)5MAsH,Ph (1 -3) in good yields. Reaction of C,H,(CO),Mn(THF) with PhAsH,, however, leads to a product mixture from which the binuclear diphenyldiarsane derivative CSH5(CO),Mn(PhHAs-AsHPh)Mn(CO),CSH, (4) has been isolated. X-ray structure analysis and epimerisation reactions of the complex-stabilized diphenyldiarsane are described.

Structural chemistry of transition metal complexes containing arsenic-arsenic bonds

“…The structural data for the cation of 51 are of low quality, but it is probable that the average As-As distance (2.42 (2) A) reveals an elongation relative to the As-As distance in 36 (2.372 (5) A) as would expected if each As uses both lone pairs in cluster formation. As expected, 51 is paramagnetic with a room-temperature magnetic moment of 2.22 mb-In reactions of cycZo-(MeAs)5 (1) with [CpMo(CO)3]2, several products are possible, depending on reaction conditions (see Scheme I). If the reactants are rapidly heated to high temperatures (175-180 °C), decarbonylation precedes demethylation, and fully substituted chains of MeAs units (e.g., 19) are formed.…”

“…Perhaps the most elegant demonstration of this comes from the same property of phosphorus atoms: Scherer has formed (pentaphosphacyclopentadienyl) (pentamethylcyclopentadienyl)iron (50) from white phosphorus and [Cp*Fe(CO)2]2. The relationship between 50 and ferrocene is obvi-50 Sacconi and co-workers have further coordinated the As3 plane in a CoAs3 tetrahedral complex in which each of the metallic groups is (triphos) Co (triphos = CH3C-(CH2PPh2)3) to form {[(triphos)Co]2(M,»?3-cycZo-As3)j-(BPh4)2 (51).81'82 Compound 51 is formed from the reaction of yellow arsenic and cobalt tetraphenylborate in the presence of triphos. The structural data for the cation of 51 are of low quality, but it is probable that the average As-As distance (2.42 (2) A) reveals an elongation relative to the As-As distance in 36 (2.372 (5) A) as would expected if each As uses both lone pairs in cluster formation.…”

Synthesen und Strukturen von Distibankomplexen / Syntheses and Structures of Distibane Complexes

“…Formen, die meso-Verbindung und das d/l-Enantiomerenpaar vorliegen: es werden in d6-Benzol jeweils zwei Signale für die Cp-Protonen beobachtet, von denen das intensivere vermutlich der sterisch günsti geren meso-Form zukommt [4], Für die Signale der Alkylsubstituenten in lb , c beobachtet man jeweils ein breites Singulett; die Stereoisomerie hat offenbar Die Verbindungen 1 sind brombeerfarbene fein kristalline Festkörper. Ihre intensive Farbigkeit ist überraschend; sie ist nicht auf Festkörpereffekte zu rückzuführen [3], da sie auch unverändert in Lösung erhalten bleibt.…”

Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex

“…We previously reported that the [U(Tren TIPS )] (Tren TIPS = N(CH 2 CH 2 NSiPr i 3 ) 3 )f ragment stabilizes reactive fragments such as cyclo-P 5 , [10] mono-oxo, [11] terminal nitrides (U N), [12] and parent U = EH groups (E = N, P, As). [13][14][15] Thel atter of these was prepared by reaction of [U(Tren TIPS )(THF)][BPh 4 ] (1) [14] with KAsH 2 , [16] to give [U(Tren TIPS )(AsH 2 )] (2) [15] followed by deprotonation of 2 and abstraction of the potassium cation by ac rown ether.I nspired by the works of Herrmann and Huttner, [17] we wondered whether 2 could undergo oxidative homocoupling to give HAsAsH stabilized by ab ulky [U(Tren TIPS )] unit that might preclude decomposition.…”