1,1-Olefin-bridged bis-(2-indenyl) metallocenes of titanium and zirconium.

Tetrasubstituted alkenes bearing geminal 2-indenyl substituents--9-[bis(1H-inden-2-yl)methylidene]-9H-fluorene (6), 2,2'-(2,2-diphenylethene-1,1-diyl)-bis(1H-indene) (7), and 2,2'-(2-propylpent-1-ene-1,1-diyl)-bis(1H-indene) (8) have been synthesized and metallated to form a new class of ansa titanium and zirconium metallocene complexes containing a single sp(2)-hybridized carbon bridge. The synthesis of the tetramethylated bis-indenyl Zr-analog is described. In addition, the 1,1-bis-indenyl ethylene is prepared and the Zr complex is modified by olefin metathesis. X-ray structure analyses reveal strained η(5) sandwich complexes with highly open metal centers. These complexes have proven active in the polymerization of ethylene and its copolymerization with 1-hexene.

Titanium "constrained geometry" complexes with pendant arene groups.

The synthesis of the proligands C(5)Me(4)HSiMe(2)N(H)R) (R = CMe(2)Ph 1, 2-C(6)H(4)Ph 2) was accomplished via a straightforward salt metathesis reaction of the appropriate lithium amide and ClSiMe(2)(C(5)Me(5)H). Generation of the dilithio salt and reaction with TiCl(3)·(THF)(3) followed by oxidation gave C(5)Me(4)SiMe(2)N(C(6)H(4)Ph)TiCl(2) (3) in low yield. In contrast, deprotonation of 1 and 2 and reaction with (Me(2)N)(2)TiCl(2) afforded C(5)Me(4)(SiMe(2)NR)Ti(NMe(2))(2) (R = CMe(2)Ph 4, 2-C(6)H(4)Ph 5), respectively, in good yields Treatment with MeI gave the analogs C(5)Me(4)(SiMe(2)NR)TiI(2) (R = CMe(2)Ph 6, 2-C(6)H(4)Ph 7). Reduction of 7 with potassium graphite afforded C(5)Me(4)(SiMe(2)NC(6)H(4)Ph)Ti 8. Treatment of 6 and 7 with MeMgBr afforded C(5)Me(4)(SiMe(2)NR)TiMe(2) (R = CMe(2)Ph 9, 2-C(6)H(4)Ph 10). Complexes 9 and 10 in combination with the activator [Ph(3)C][B(C(6)F(5))(4)] catalyzed the polymerization of styrene and ethylene. Copolymerization was also investigated. While the catalyst derived from 10 showed poor activity, compound 9 showed markedly higher activity than 10 and (C(5)Me(4))SiMe(2)(NtBu)]TiMe(2).

Ring-opening of cyclopropanes by "frustrated Lewis pairs".

Reactions of phosphine/borane frustrated Lewis pairs with cyclopropanes result in the ring opening, yielding phosphonium borate products.

Rapid assembly of vinigrol's unique carbocyclic skeleton.

Detailed in this account are our efforts toward the total synthesis of vinigrol. A highly expedient and convergent synthetic approach made possible by the use of a strategic oxidative dearomatization reaction coupled with a series of ensuing substrate controlled transformations is discussed.

Synthesis and explosive decomposition of organometallic dehydro[18]annulenes: an access to carbon nanostructures.

The synthesis of eight new cyclobutadiene or ferrocene-fused organometallic dehydroannulenes is reported. Cadiot-type coupling of a 1-bromoethynyl-2-silylethynylbenzene derivative to an organometallic diyne (1,2-diethynyl-3,4-bis(trimethylsilyl)cyclobutadiene(cyclopentadienyl )cobalt or 1,2-diethynylferrocene) is followed by deprotection and Cu(OAc)(2)-promoted ring closure. Five of the organometallic dehydroannulenes were structurally characterized. Three of the novel cycles explode at temperatures from 196 to 293 degrees C and form insoluble carbon materials. The soot produced from 13a shows a high abundance of onion-like carbon nanostructures. The nanostructures were characterized by high-resolution transmission electron microscopy.