Abstract
The organometallic chemistry of metal complexes with organocyclic ligands of higher than five hapticity is much more lacking than the chemistry of metal complexes with η5-cyclopentadienyl ligands, which has been explored in considerable depth, resulting in novel advances. The main reason for this is stability. In particular, reports indicate that (η7-C7H7)MLn complexes are considerably less stable than analogous (η5-C5H5)MLn. In perfluoroalkyl metal chemistry, there is currently no reported (η7-C7H7)MLn derivative, whereas a number of alkylated ones are known and important conclusions have been drawn about their stability. Responding to this void, and using Morrison’s trifluoromethylating reagent, the present study reports the synthesis and characterization of the first cycloheptatrienyl molybdenum complexes bearing the trifluoromethyl moiety; (η7-C7H7)Mo(CO)2CF3 (I), and (η7-C7H7)Mo(CO)(PMe3)CF3 (II) and discusses their low thermal instability.
Highlights
Molecules 2021, 26, 6838. https://The interest in the chemistry of the trifluoromethyl group is both theoretical and industrial as the demand for compounds containing CF3 moieties is high due to their applications in advanced materials, pharmaceuticals, agrochemicals, fluorous chemistry, and medicine [1,2]
It is well known that systems of (η5 -C5 H5 )MLn (M = transition metal, Ln = n-ligands) are ubiquitous in organometallic chemistry and as reports suggest of much higher stability than analogous systems with carbocyclic ligands of with higher hapticity, such as (η7 -C7 H7 )MLn [8]
We report hereinand the characterization of the first η7 -cycloheptatrienlyl trifluoromethyl molybdenum complexes, 7-cycloheptatrienlyl trifluoromethyl molybsynthesis and characterization of the first η (η7 -C7 H7 )Mo(CO)2 CF37 (I) and (η7 –C7 H7 )Mo(CO)(PMe
Summary
Molecules 2021, 26, 6838. https://The interest in the chemistry of the trifluoromethyl group is both theoretical and industrial as the demand for compounds containing CF3 moieties is high due to their applications in advanced materials, pharmaceuticals, agrochemicals, fluorous chemistry, and medicine [1,2]. Despite the interest, the number of transition metal complexes bearing perfluoroalkyl ligands is small. This is especially evident if their number is compared with the that of the alkyl counterparts [3]. The plethora of known alkylated transition metal complexes and the efficiency of their preparation methods has made possible several extremely important advances in both theoretical and practical application chemistry of the C-H bond, with most notable being the study of. It is well known that systems of (η5 -C5 H5 )MLn (M = transition metal, Ln = n-ligands) are ubiquitous in organometallic chemistry and as reports suggest of much higher stability than analogous systems with carbocyclic ligands of with higher hapticity, such as (η7 -C7 H7 )MLn [8]. The complex (η7 -C5 H5 )Mo(CO) CH3 is indefinitely air stable and melts at 145 ◦ C without decomposition [10,11]
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