Insertion Reactions into the Boron鈥揃oron Bonds of Barrelene-Type 1,2-Diaminodiboranes(4)
详细信息 查看全文
- 作者：Steffen Pospiech ; Michael Bolte ; Hans-Wolfram Lerner ; Matthias Wagner
- 刊名：Organometallics
- 出版年：2014
- 出版时间：December 8, 2014
- 年：2014
- 卷：33
- 期：23
- 页码：6967-6974
- 全文大小：410K
- ISSN：1520-6041
文摘
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 掳C, both compounds cleanly insert a Pt(PEt3)2 moiety into their B鈥揃 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鈥?tBu)C鈺怌(H)鈥揃-bridged 9,10-DHA 3 and Pt(畏2-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鈥揅(鈺怤R)鈥揃 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鈥揅-bridged 9,10-DHA 8 was observed.