Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH und (C₁₈H₃₆N₂O₆Na₂)₂[Mo₆Cl₈(OC₆H₅)₆]

Abstract

Die Umsetzung von Na2[Mo6Cl8(OCH3)6] mit 2,2,2‐crypt führt zu (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6 CH3OH (1), aus dem durch Metathese mit Phenol (C18H36N2O6Na)2[Mo6Cl8(OC6H5)6] (2) dargestellt wird. Nach Strukturbestimmungen an Einkristallen (1): P31 c, a=14,613(3) Å, c=21,036(8) Å; 2: P31c, a=15,624(1) Å, c=19,671(2) Å liegen in den Verbindungen Clusteranionen vom Typ [Mo6Cl8i(ORa)6]2− vor (1: d(Mo—Mo) 2,608(1) Å bis 2,611(1) Å, d(Mo—Cl) 2,489(1) Å bis 2,503(1) Å, d(Mo—O) 2,046(4) Å; 2: d(Mo—Mo) 2,602(3) Å bis 2,608(3) Å, d(Mo—Cl) 2,471(5) Å bis 2,492(5) Å, d(Mo—O) 2,091(14) Å). Die elektronischen Wechselwirkungen zwischen dem Halogenidcluster und den Phenolatliganden in [Mo6Cl8(OC6H5)6]2− werden durch UV/VIS‐Spektroskopie untersucht und mit Hilfe von EHMO‐Rechnungen analysiert.

(C18H36N2O6Na)2[Ta6Cl12(CH3O)6].6CH3OH with partial substitution of CH3O− by OH−

“…Despite the small distortion of the octahedron, all Ta--CI distances are identical (2.448 _+0.001 A) within the precision of the structure determination. Six methanol molecules are connected to the anion via O(1)...H(9)--O(2) hydrogen bonds [O(1)...O(2) = 2.684 (15)/~], as similarly observed in the structure of (CIsH36NzO6Na)z[Mo6CIs(CH30)6].-6CH3OH, which contains an [Mo6Cls(CH30)6] zanion (Perchenek & Simon, 1993). The anionic unit is, in certain details, e.g.…”

“…In the course of experiments aimed at the preparation of [Ta6CI~2] 4÷ clusters with the anions of thermally labile alcohols as outer ligands we attempted to adapt the method developed by Perchenek & Simon (1993)…”

Hybrid organic–inorganic, hexa-arm dendrimers based on an Mo6Cl8 core

“…These six arm, pseudooctahedral core dendrimers represent one of the first examples of this type. 12 The replacement of both methoxy by other alkoxy ligands [13][14][15][16] and of triflate by other alkoxy or carboxy ligands 17,18 at the corner positions of these clusters have been reported. Here, the use of such reactions in the synthesis of new hybrid organic-inorganic macromolecules is illustrated.…”

“…Using a modification of conditions reported in the literature, [13][14][15][16]22 reaction of the ligands L0, L1 and L2 with Na 2 [Mo 6 Cl 8 (OCH 3 ) 6 ] resulted in complete exchange for all molecules prepared. In the case of Na 2 G0, a 98% yield of an analytically pure product was obtained, and crystals suitable for X-ray structure determination were obtained (Fig.…”

“…Mo-Cl 2.48-2.50 Å, Mo-O 2.04-2.09 Å). 13,16,24 Dendrimers were characterized by NMR and mass spectrometry (MS). We found electrospray MS to be most convenient as a strong parent ion signal could be obtained.…”