abstract
The reactions of [Mo(CO)(2)(Cp)(NCCH3)(2)][BF4] (1) with spiro[2.4]hepta-4,6-diene and spiro[4.4]nona-1,3-diene give the complexes [Mo{eta(4)-C5H4(CH2)(2)}(CO)(2)(Cp)][BF4] (3) and [Mo{eta(4)-C5H4(CH2)(4)}(CO)(2)(Cp)][BF4] (4), respectively. [Mo{eta(4)-C5H4(CH2)(2)}(CO)(2)(Cp)][BF4] (3) is stable towards ring opening at room temperature, but its formation is accompanied by small amounts of ring-opening products [Mo(eta(5)-C5H4CH2-eta(1)-CH2)(CO)(Cp)][BF4] (5) and [Mo(eta(5)-C5H4(CH2)(2)-eta(4)-CO}(CO)(Cp)][BF4] (6). With 1,1-dimethylspiro[2.4]hepta-4,6-diene, two isomers with the formula [Mo{eta(4)-C5H4CH2C(CH3)(2)}(CO)(2)(CP)][BF4] are formed (7 and 8). While the endo-isomer 7 is stable towards ring opening, the exo-isomer 8 slowly rearranges to the ring-opened product [Mo{eta(5)-C5H4C(CH3)(2)CH2-eta 1'-CO}(CO)(Cp)][BF4] (9). The reaction of [Mo(CO)(2)(Ind)(NCCH3)(2)][BF4] (2) with spiro[4.4]nona-1,3-diene also gives the diene coordinated species [Mo{eta(4)- C5H4(CH2)(4)}(CO)(2)(Ind)][BF4] (11), which is the first example of a structurally characterized, coordinated, unsubstituted spirodiene. In contrast, reaction of 2 with spiro[2.4]hepta-4,6-diene leads directly to the ansa-cyclopentadienyl complex [Mo(eta(5)-C5H4CH2-eta(1)'-CH2)(CO)(Ind)][BF4] (12). Reaction of 12 with bromine or iodine leads to the formation of Cp-substituted molybdenocene derivatives [Mo{eta(5)-C5H4(CH2)(2)X}(CO)(Ind)X][BF4] (13: X = Br, 14: X = 1). The compounds [Mo(eta(5)-C5H4CH2-eta(1)'-CH2)(CO)(Ind)][BF4] (12) and [MoBr{eta(5)-C5H4(CH2)(2)Br}(CO)(Ind)][Br)center dot 0.5H(2)O (13a) were structurally characterized, and they open the way to new functionalized molybdenocene complexes that have biological applications. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007.
keywords
CAMBRIDGE STRUCTURAL DATABASE; MOLYBDOCENE DICHLORIDE; MIXED-RING; TITANOCENE DICHLORIDE; INDENYL ANALOGS; TITANIUM DICHLORIDE; OPENING REACTIONS; CYCLOPENTADIENYL; DERIVATIVES; SPIRO<2.4>HEPTA-4,6-DIENE
subject category
Chemistry
authors
Honzicek, J; Paz, FAA; Romao, CC
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