9,10-Dihydroanthracene-9,10-diyl-bridged B(2)(NMe(2))(2) readily adds [H(2)NMe(2)](+), HCl and F(3)CCOOH across its partial B=N double bond(s), thereby forming mono- or diadducts; treatment with 1-iso-propyl-2-mercaptoimidazole leads to a triply B-B-bridged propellane-like structure.
Double lithiation of 9,10-dihydroanthracene
(DHA) or 6,13-dihydropentacene
(DHP) with nBuLi, followed by the addition of B2(NMe2)2Cl2, affords 9,10-DHA-9,10-diyl-
(1a) or 6,13-DHP-6,13-diyl-bridged B2(NMe2)2 (1p) in good yields. Upon treatment
with Pt(PEt3)3 in C6H6 at 60 °C, both compounds cleanly insert a Pt(PEt3)2 moiety into their B–B bonds to furnish the corresponding
diboryl Pt(II) complexes 2a and 2p. Compound 2a reacts with excess tBuCCH to give an equimolar
mixture of the B–(tBu)CC(H)–B-bridged
9,10-DHA 3 and Pt(η2-tBuCCH)(PEt3)2 (4). The addition
of isocyanides to either the Pt(II) complex 2a or the
Pt-free species 1a yields bicyclic products, in which
a 9,10-DHA-9,10-diyl fragment is spanned by a B–C(NR)–B
linker (R = tBu (5), iPr (6)). Both 5 and 6 are
extremely prone to hydrolysis. In the case of 6, a water-induced
rearrangement reaction leading to a B–C-bridged 9,10-DHA 8 was observed.
9,10-(Bpin)2-anthracene (3, HBpin = pinacolborane) was synthesized from 9,10-dibromoanthracene in a stepwise lithiation/borylation sequence. The reaction of 3 with highly activated magnesium furnished the diborylated magnesium anthracene 4, which was quenched in situ with ethereal HCl to yield cis-9,10-(Bpin)2-DHA (cis-5, DHA = 9,10-dihydroanthracene). Compound cis-5, in turn, can be reduced with Li[AlH4] in THF to give its diborate Li2[cis-9,10-(BH3)2-DHA] (Li2 [cis-6]). In the crystal lattice, the THF solvate Li2[cis-6]⋅3 THF establishes a dimeric structure with Li-(μ-H)-B coordination modes. Hydride abstraction from Li2[cis-6] with Me3SiCl yields the B-H-B-bridged DHA Li[7]. This product can also be viewed as a unique cyclic B2H7(-) derivative with a hydrocarbon backbone. Treatment of Li2[cis-6] with the stronger hydride abstracting agent Me3SiOTf (HOTf = trifluoromethanesulfonic acid) in THF affords the THF diadduct of cis-9,10-(BH(OTf))2-DHA.
The title molecule, C34H28I4·4C6H6, has crystallographic symmetry and crystallizes with four symmetry-related benzene solvent molecules. The phenyl group is eclipsed with one of the adamantane C—C bonds. The tetraphenyladamantane units and the benzene solvent molecules are connected by weak intermolecular phenyl–benzene C—H⋯π and benzene–benzene C—H⋯π interactions. In the crystal, molecules are linked along the c-axis direction via the iodophenyl groups by a combination of weak intermolecular I⋯I [3.944 (1) Å] and I⋯π(phenyl) [3.608 (6) and 3.692 (5) Å] interactions.
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