The dimeric complex di-μ-chlorodichloro-bis[(1−3η:6−8η)-2,7-dimethyloctadienediyl]diruthenium(IV) in the presence of base reacts with cyclic and acyclic dienes to the corresponding
bis(η5-dienyl)ruthenium(II) compounds. Crystalline yellow compounds have been isolated
in high yields for dienyl = cyclopentadienyl, pentamethylpentadienyl, cycloheptadienyl,
indenyl, dimethylpentadienyl, and trimethylpentadienyl. The analogous reaction of cyclohexa-1,3-diene gives the ruthenium(0) compound (η6-benzene)(η4-cyclohexa-1,3-diene)ruthenium.
The “open” bis(dienyl)ruthenium complexes can be converted into half-sandwich complexes
through protonation and subsequent ligand exchange. These compounds can be used as
precursors for efficient enantioselective hydrogenation catalysts.
A novel and versatile approach has led to the synthesis of various classes of mono-and bidentate phospholane and phosphinite ligands based on a benzothiophene scaffold. The ligand functions in the bidentate ligands can be introduced independently and consecutively. A bis-phospolane ligand as well as its rhodium complex have been characterized by[a] CIBA SC, K-420.2.20, Ligands of type 19a or 19b are of interest for hydroformylation reactions and initial results for the hydroformylation of vinyl acetate and styrene look promising. [26] www.eurjoc.org
Addition compounds of MoO 2 Br 2 are useful precursors for the synthesis of species that are relevant in catalytic chemical and biochemical oxotransfer processes. 1 Also, molybdenum bromides are on the borderline of stability for þ 5 and þ 6 oxidation states of the metal, which makes them potentially useful for redox studies. These compounds are usually prepared by treating MoO 2 Br 2 with the appropriate ligand in aprotic solvents, 2 and in a few cases by addition of the ligand to a solution of H 2 MoO 4 Á H 2 O in HBr. 3 However, the presence of MoO 2 Br 2 (H 2 O) 2 in solutions of alkali molybdates in concentrated hydrobromic acid 4 and the extractability of this species with diethyl ether suggest that a number of addition compounds could be readily accessible from commercial sodium molybdate. In this manner a number of adducts with O-donor ligands can be isolated. 5 Here we describe the preparation of the outer-sphere, hydrogen-bonded complex MoO 2 Br 2 (H 2 O) 2 Á diglyme as well as those of the adducts MoO 2 Br 2 (L) 2 ,
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