Reactions of the Heavier Group 14 Element Alkyne Analogues Ar‘EEAr‘ (Ar‘ = C<sub>6</sub>H<sub>3</sub>-2,6(C<sub>6</sub>H<sub>3</sub>-2,6-Pr<i><sup>i</sup></i><sub>2</sub>)<sub>2</sub>; E = Ge, Sn) with Unsaturated Molecules: Probing the Character of the EE Multiple Bonds
作者:Chunming Cui、Marilyn M. Olmstead、James C. Fettinger、Geoffrey H. Spikes、Philip P. Power
DOI:10.1021/ja055372s
日期:2005.12.1
of formula Ar'Ge3+(TCNE)2-}3(GeAr')+}3. The digermyne 1 also reacted with 1 equiv of PhCPh to give the 1,2-digermacyclobutadiene 12, which has a ring, and with Me(3)SiCCH or PhCC-CCPh to activate a flanking C6H3-2,6-Pr(i)2 ring and give the tricyclic products 13 and 14. The "distannyne" 2 did not react with these acetylenes. Overall, the experiments showed that 1 is highlyreactive toward unsaturated
描述了炔类似物 Ar'EEAr' (Ar' = C6H3-2,6(C6H3-2,6-Pr(i)2)2; E = Ge (1); Sn (2)) 与不饱和分子的反应. 1 和 2 与偶氮苯反应得到新的肼衍生物 Ar'E(Ph)NN(Ph)}EAr' (E = Ge (3); Sn (4))。用 Me3SiN3 处理 1 得到环状单线态双自由基 Ar'Gemu2-(NSiMe3)}2GeAr' (5),而 2 得到单酰亚胺桥连的 Ar'Snmu2-N(SiMe3)}SnAr' (6)。1 与 t-BuNC 或 PhCN 反应生成加合物 Ar'GeGe(CNBu(t))Ar' (7) 或环化合物 (8)。相反,锡化合物 2 不与 t-BuNC 或 PhCN 反应。用 N2CH(SiMe3) 处理 1 生成的 Ar'Gemu2-CH(SiMe3)}mu2:eta2-N2CH(SiMe3)
Reversible complexation of isocyanides by the distannyne Ar′SnSnAr′ (Ar′ = C6H3-2,6(C6H3-2,6-iPr2)2)
作者:Yang Peng、Xinping Wang、James C. Fettinger、Philip P. Power
DOI:10.1039/b919828h
日期:——
The reaction of the distannyne Ar'SnSnAr' (Ar' = C(6)H(3)-2,6(C(6)H(3)-2,6-(i)Pr(2))(2)) with tert-butyl or mesityl isocyanide afforded the bis-adducts Ar'SnSnAr'(CNBu(t))(2) or Ar'SnSnAr' (CNMes)(2) in which the isonitriles are reversibly bound under ambient conditions.
The Role of Group 14 Element Hydrides in the Activation of C–H Bonds in Cyclic Olefins
作者:Owen T. Summerscales、Christine A. Caputo、Caroline E. Knapp、James C. Fettinger、Philip P. Power
DOI:10.1021/ja305853d
日期:2012.9.5
(excess), compounds ArE(CH(2)CH(2)tBu)}(2) [E = Ge(8), Sn(9)] are obtained in addition to ArECp; in the case of CpH, the neohexyl complexes replace the production of H(2) gas, and for c-C(5)H(8) they displace cyclopentyl product 5 and account for all the hydrogen removed in the dehydroaromatization reactions. To confirm the source of 8 and 9, it was demonstrated that these molecules are formed cleanly between
形式上,三键二金属炔ArEEAr [E = Ge (1), Sn (2); Ar = C(6)H(3)-2,6-(C(6)H(3)-2,6-(i)Pr(2))(2)] 先前已被证明可激活脂肪族、烯丙基环状烯烃、环戊二烯 (CpH)、环戊烯 (cC(5)H(8)) 和 1,4-环己二烯中的 CH 键,具有令人感兴趣的选择性。在五元碳环的情况下,形成环戊二烯基物质 ArECp [E = Ge (3), Sn (4)]。在这项研究中,我们使用实验方法检查了 CpH 和 cC(5)H(8) 的活化机制,并描述了从 1 和 cC(5)H(8) 之间的反应中发现的新产品,一种不对称取代的二锗烯 ArGe (H)Ge(cC(5)H(9))Ar (5),以 46% 的产率结晶。该化合物含有氢化环戊基部分,发现以 3:2 的比例与 3、解释了三重 CH 活化后释放的 H 原子的命运。我们表明,当这些 CH
Metathetical Exchange between Metal–Metal Triple Bonds
作者:Joshua D. Queen、Alice C. Phung、Christine A. Caputo、James C. Fettinger、Philip P. Power
DOI:10.1021/jacs.9b13604
日期:2020.2.5
condi-tions (≤80°C, 1 bar) afforded AriPr4M≡MoCp(CO)2 or AriPr6M≡MoCp(CO)2 in moderate to excellent yields. The reactions represent the first isolable products from a me-tathesis of two metal-metal triplebonds. Analogous ex-change reactions with the single-bonded (CO)3CpMo-MoCp(CO)3 gave ArM̈-MoCp(CO)3 (Ar = AriPr4 or AriPr6 ; M = Sn or Pb). The products were characterized by NMR (1H, 13C, 119Sn, or 207Pb)
Different reactivity of the heavier group 14 element alkyne analogues Ar′MMAr′ (M = Ge, Sn; Ar′ = C6H3-2,6(C6H3-2,6-Pri2)2) with R2NO
作者:Geoffrey H. Spikes、Yang Peng、James C. Fettinger、Jochen Steiner、Philip P. Power
DOI:10.1039/b513189h
日期:——
Ar'MMAr' (M = Ge or Sn) with R2NO, (R2NO = Me2C(CH2)3CMe2NO or N2O), result in complete MM bond cleavage to afford the germylene :Ge(Ar')ONR2 or the germanium(II) or tin(II) hydroxides M(Ar')(micro-OH)}2.