Molybdänhalogenidcluster mit zwei terminalen Alkoholatliganden: Synthese und Kristallstrukturen von (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OCH₃)₂] und (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₁₂(OC₁₅H₁₁)₂] · 2C₄H₆O₃

Abstract

Die Reaktion von Mo6Cl12 mit zwei Äquivalenten Natriummethanolat führt in Gegenwart von 2,2,2‐crypt zu (C18H36N2O6Na)2[Mo6Cl12(OCH3)2] (1). Durch Metathese von 1 mit 9‐Anthrylmethanol in Propylencarbonat wird (C18H36N2O6Na)2[Mo6Cl12(OC15H11)2] · 2C4H6O3 (2) erhalten. Die Strukturbestimmung an Einkristallen (1: C2/m, a=25,513(8) Å, b=13,001(3) Å, c=10,128(3) Å, β=100,204(12)°; 2: C2/c, a=15,580(5) Å, b=22,337(5) Å, c=27,143(8) Å, β=98,756(10)°) zeigt, daß in beiden Verbindungen Clusteranionen der Zusammensetzung [Mo6Cl 8iCl 4a(ORa) 2]2− mit zwei zueinander trans‐ständigen terminalen Alkoholatliganden vorliegen (1: d(Mo—Mo) 2,597(2) Å bis 2,610(2) Å, d(Mo—Cli) 2,471(3) Å bis 2,493(4) Å, d(Mo—Cla) 2,417(8) Å und 2,427(8) Å, d(Mo—O) 2,006(13) Å; 2: d(Mo—Mo) 2,599(3) Å bis 2,628(3) Å, d(Mo—Cli) 2,468(8) Å bis 2,506(7) Å, d(Mo—Cla) 2,444(8) Å bzw. 2,445(7) Å, d(Mo—O) 2,012(19) Å).

Synthesis of hexanuclear molybdenum clusters containing phosphine oxide ligands

“…Even though there is a large difference between the Mo-Cl terminal bond lengths, they are still within the observed range for previously reported terminal Mo-Cl bond lengths in structurally similar cluster complexes (2.4018(22)-2.445(7) Å). 8,17, 18 In addition, the bond lengths of the 24 electron cluster core are similar to those reported for other [Mo 6 (µ 3 -Cl of these redox processes are assigned as single electron processes. 29 The redox potentials for the tertiary phosphine oxide cluster complexes appear at more positive potentials as compared to the [Mo 6 (µ 3 -Cl) 8 Cl 6 ] 2Ϫ complex, which is expected based on the difference in the overall charges of these cluster complexes.…”

Synthesis, Structures, and Redox Properties of Octa(μ3-sulfido)hexarhenium(III) Complexes Having Terminal Pyridine Ligands

“…Cr 12 S 16 (PEt 3 ) 5 has been reported recently . Di- and trisubstituted halogeno-capped clusters [Mo 6 Cl 8 Cl 4 X 2 ] n - ( n = 0, X = DMF, DMSO, PEt 3 ; , n = 2, X = OCH 3 , OCH 2 C 14 H 9 ) and [Mo 6 Cl 8 Cl 3 (PEt 3 ) 3 ] - , respectively, are also known.…”

“…Cr 12 S 16 (PEt 3 ) 5 has been reported recently. 32 Di-and trisubstituted halogenocapped clusters [Mo 6 Cl 8 Cl 4 X 2 ] n-(n ) 0, X ) DMF, DMSO, 33 PEt 3 ; 34,35 n ) 2, X ) OCH 3 , OCH 2 C 14 H 9 ) 36 and [Mo 6 Cl 8 Cl 3 -(PEt 3 ) 3 ] -, 25 respectively, are also known. Hexanuclear rhenium clusters with chalcogenido caps (S, Se, Te) are the most recently developed among the complexes with the hexanuclear motifs.…”

A One-Dimensional Array of Clusters: Na2Mo6Cl8(O2CC5H4FeCp)6·CH3OH

“…The Na + ions are related by a center of inversion and each is coordinated to a total of three carboxylate groups (one from a neighboring cluster) and one methanol molecule, Figure . Na−O distances in this structure are much shorter than those of an 8-coordinated sodium cryptate where d (Na−O) values range from 2.492 to 2.561 Å . The short Na−O distances indicate strong interactions between the cluster-bound carboxylate and the bridging Na + cations.…”

“…The sodium and sodium cryptate salts of the mixed-metal cluster [Mo 6 Cl 8 (O 2 CC 5 H 4 FeCp) 6 ] 2- are readily synthesized from the appropriate salt of [Mo 6 Cl 8 (OMe) 6 ] 2- and ferrocenecarboxylic acid, HO 2 CC 5 H 4 FeCp. [Mo 6 Cl 8 (OMe) 6 ] 2- reacts readily with proton sources and has been used as a starting material for generating clusters with aromatic alkoxide ( - OAr) ligands, [Mo 6 Cl 8 (OAr) 6 ] 2- . , The sodium and the sodium cryptate salt of the new ferrocenecarboxylate cluster have solubilities comparable to those of other − [Mo 6 Cl 8 ] 4+ clusters with similar counterions: insolubility in CH 3 CN, slight solubility in methanol, and high solubility in dimethylformamide and dimethyl sulfoxide. Cyclic voltammetry of (cryptNa) 2 [Mo 6 Cl 8 (O 2 CC 5 H 4 FeCp) 6 ] indicates that the ferrocenecarboxylate ligands are not displaced by either DMF or DMSO.…”