Mono- and dinuclear molybdenum complexes with sterically demanding cycloheptatrienyl ligands

Dalton Transactions : an International Journal of Inorganic Chemistry
Matthias TammMareike Gerenkamp

Abstract

Sterically demanding cycloheptatrienylium (tropylium) salts of the type (1,3,5-C7H4R3)BF4 [R = t-Bu, (3a)BF4; R = SiMe3, (3b)BF4] have been prepared from the corresponding 1,3,5-trisubstituted benzene derivatives 1 by ring expansion with diazomethane followed by hydride abstraction with triphenylcarbenium tetrafluoroborate, (Ph3C)BF4. Complexation can be achieved by arene exchange and Mo(CO)3 group transfer employing [(eta6-p-xylene)Mo(CO)3] (4) to yield the cationic complexes (5)BF4. In refluxing mesitylene, [(eta7-C7H4t-Bu3)Mo(CO)3]BF4, (5a)BF4, undergoes CO substitution to furnish the mesitylene sandwich complex (6a)BF4. A cyclic voltammetric study reveals that this complex exhibits a reversible one-electron oxidation to the dicationic 17e complex 6a2+, which can also be accessed by chemical oxidation with AgBF4. On the contrary, the reduction of 6a+ is irreversible and does not yield a stable 19e complex 6a. To study the fate of the reduced 19e form, (5a)BF4 was treated with Na2Hg to diastereoselectively afford the C-C coupled bicycloheptatriene complex 7a. Paramagnetic, dinuclear complexes of the type [(eta7-C7H4R3)Mo(mu-Cl)3Mo(eta7-C7H4R3)] (8) have been obtained from the reaction of (5)BF4 with Me3SiCl. These can be rega...Continue Reading

References

Jan 1, 1995·Acta Crystallographica. Section A, Foundations of Crystallography·R H Blessing
Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
Oct 29, 2000·The Journal of Organic Chemistry·M TammR Frohlich
Jan 10, 2002·Inorganic Chemistry·Matthias TammChristiane Holst
Jun 13, 2002·Chemical Reviews·Frank T EdelmannHerbert Schumann
Feb 15, 1999·Angewandte Chemie·George J P BritovsekDuncan F Wass

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Citations

Jan 1, 2008·Acta Crystallographica. Section E, Structure Reports Online·Peter G JonesMatthias Tamm

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