Reaction of Spiro 2.4 hepta-4,6-diene with Molybdenum(II) Indenyl Compounds: Effects of Substitution in the Indenyl Ligand

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Abstract

The series of molybdenum indcnyl compounds [(Ind')Mo(CO)(2)(NCMe)(2)][BF4] was prepared, and their reactivity toward spiro[2.4]hepta-4,6-diene was studied. It was observed that the spiro[2.4]hepta-4,6-diene ring opening could be blocked through substitution in the indenyl ring. Hence, the 2-substituted compound [(eta(5)-C9H6Me)Mo(CO)(2)(NCMe)(2)][BF4] and 1,3-disubstituted compound [(eta(5)-(C9H5Bu2)-Bu-t)Mo(CO)(2)(NCMe)(2)][BF4] do not produce the usual ansa-compounds but the compounds with eta(4)-bonded spiro[2.4]hepta-4,6-diene [(Ind')(eta(4)-C5H4(CH2)(2))Mo(CO)(2)][BF4]. The use of 1-substituted compounds [(eta(5)-C9H6R)Mo(CO)(2)(NCMe)(2)][BF4] (R = Ph, Bu-t) or compounds with less sterically demanding substituents in the 1,3-positions [(eta(5)-C9H5Ph2)Mo(CO)(2)(NCMe)(2)][BF4] does not block the ring-opening reaction. These compounds give ansa-molybdenocenes [(Ind')(eta(5)-C5H4CH2-eta(1)-CH2)Mo(CO)][BF4] in a manner similar to that for the unsubstituted analogue. The reaction products were characterized by NM R and I R spectroscopy. Structures of [(eta(5)-C9H5Ph2)Mo(eta(3)-C3H5)(CO)(2)], [(eta(5)-C9H6Ph)(eta(5)-C5H4CH2-eta(1)-CH2)Mo(CO)][BF4], and [(eta(5)-C9H5Ph2)(eta(5)-C5H4CH2-eta(1)-CH2)Mo(CO)][BF4] were determined by single-crystal X-ray analysis.
Original languageUnknown
Pages (from-to)714-722
JournalOrganometallics
Volume30
Issue number4
DOIs
Publication statusPublished - 1 Jan 2011

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