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Synthesis and characterization of cis-[Mo{sub 6}Cl{sub 8}(Cl{sub 4})(P(C{sub 2}H{sub 5}){sub 3}){sub 2}]{center_dot}2THF

Journal Article · · Inorganic Chemistry
; ;  [1]
  1. Cornell Univ., Ithaca, NY (United States); and others

The chemistry of group 6 clusters of the type [M{sub 6}Cl{sub 8}X{sub 6}]{sup 2-}(M=Mo, W; X = Br{sup -}, Cl{sup -}, I{sup -}, OH{sup -}, SCN{sup -}, etc.) or [M{sub 6}Cl{sub 8}L{sub 6}]{sup 4+} (M = Mo, L = phosphine oxide, pyridine N-oxide, DMF, etc.) has been well developed over the last 50 years as many groups have explored the ligand substitution chemistry and properties of this large family of compounds. Recently, the preparation of a versatile starting material for the preparation of substituted Mo{sub 6}Cl{sub 8}{sup 4+} clusters, (Bu{sub 4}N){sub 2}[Mo{sub 6}Cl{sub 8}(CF{sub 3}SO{sub 3}){sub 6}], and a number of derivatives was reported. The halide-substituted clusters have been thoroughly investigated, and compounds with a wide variety of donor ligands are also known. In these compounds, similar to the majority of the known Mo{sub 6}Cl{sub 8}{sup 4+} complexes, all the X ligands are not identical, and most of these complexes are ligated in a trans fashion. For example, Saito et al. have prepared the trans phosphine ligated clusters trans-[Mo{sub 6}Cl{sub 8}(Cl{sub 4})(PR{sub 3}){sub 2}] R = n-C{sub 3}H{sub 7}, n-C{sub 4}H{sub 9}, n-C{sub 5}H{sub 11}. Moreover, Perchenek and Simon have prepared the trans alcoholate ligated clusters trans-[Mo{sub 6}Cl{sub 8}X{sub 6}]{sup 2-} cluster, cis-[Mo{sub 6}Cl{sub 8}(Cl{sub 4})(P(n-C{sub 3}H{sub 7}){sub 3}){sub 2}], in 3% yield. Here, the authors report a modification of Saito`s preparation which allows the preparation of cis-ligated Mo{sub 6-} Cl{sub 8}{sup 4+} clusters in high (97%) yield.

Sponsoring Organization:
USDOE
OSTI ID:
450685
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 9 Vol. 34; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English