Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl) quinoline: Hydrolysis and Coordination to Cu~I, Ag~I and Pd~(II)

Son J.-H.; Pudenz M.A.; Hoefelmeyer J.D.

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Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl) quinoline: Hydrolysis and Coordination to Cu~I, Ag~I and Pd~(II)

机译：双功能双亲分子8-（二甲磺酰基）喹啉的反应性：水解和配位形成Cu〜I，Ag〜I和Pd〜（II）

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The ambiphilic molecule 8-(dimesitylboryl)quinoline (1) was synthesized by treatment of 8-bromoquinoline or 8-iodoquinoline with n-BuLi followed by dimesitylboronfluoride. Hydrolysis of 1 is unusually rapid compared to bulky triorganoboranes with the sequential loss of mesitylene and formation of mesityl(quinolin-8-yl)borinic acid (2) and 8-quinoline boronic acid dimer (3). Cooperativity within the bifunctional ambiphilic site leads to water activation and protodeboronation of the B-C(Mes) bonds. Blocking of the ambiphilic site of 1 by methylation of the quinoline nitrogen atom leads to an air-stable N-methyl-quinolinium salt. Coordination complexes were formed by reaction of 1 with CuCl, Ag(OTf), and PdCl_2(PhCN)_2 with coordination of the quinolinyl nitrogen to the metal ion. The Cu~I and Ag~I centers are stabilized by η~3-BC_(ipso)C_(ortho) π-interaction. The isolated Pd~(II) complex is a product of cyclometalation, resulting from elimination of HCl upon deprotonation of the ortho-methyl group of nearby mesityl. The bonding in 7 could be understood as a 16-electron Pd complex that features an anionic η~3-C _(ipso)-C_(ortho)-C_(benzyl) allylic ligand fragment plus a Pd→B bond, or an η~4-BC_(ipso)-C _(ortho)-C_(benzyl) boratabutadiene anion fragment.

机译：通过用n-BuLi然后再用氟化二苯甲磺隆处理8-溴喹啉或8-碘喹啉，合成了歧义分子8-（二甲磺酰基）喹啉（1）。与庞大的三有机硼烷相比，1的水解异常迅速，具有相继的亚甲基三甲苯损失并形成三甲基（喹啉-8-基）硼酸（2）和8-喹啉硼酸二聚体（3）。双功能歧义位点内的协同作用导致水活化和B-C（Mes）键的原脱硼氢。通过喹啉氮原子的甲基化封闭1的歧义位点会导致形成空气稳定的N-甲基-喹啉鎓盐。通过1与CuCl，Ag（OTf）和PdCl_2（PhCN）_2的反应形成配位配合物，其中喹啉基氮与金属离子配位。 Cu〜I和Ag〜I中心通过η〜3-BC_（ipso）C_（邻位）π相互作用而稳定。分离出的Pd〜（II）配合物是环金属化的产物，是由于附近邻苯三甲的邻甲基去质子化后消除了HCl而导致的。 7中的键可以理解为16电子的Pd络合物，其特征是阴离子η〜3-C_（ipso）-C_（邻）-C_（苄基）烯丙基配体片段加上Pd→B键或η 〜4-BC_（ipso）-C_（邻）-C_（苄基）硼氢化丁二烯阴离子片段。

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《Dalton transactions: An international journal of inorganic chemistry》 |2010年第45期|共10页
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Son J.-H.; Pudenz M.A.; Hoefelmeyer J.D.;
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1. Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl) quinoline: Hydrolysis and Coordination to Cu~I, Ag~I and Pd~(II) [J] . Son J.-H., Pudenz M.A., Hoefelmeyer J.D. Dalton transactions: An international journal of inorganic chemistry . 2010,第45期

机译：双功能双亲分子8-（二甲磺酰基）喹啉的反应性：水解和配位形成Cu〜I，Ag〜I和Pd〜（II）
2. Direct arylation catalysis with chloro[8-(dimesitylboryl)quinoline-κN]copper(I) [J] . Sem Raj Tamang, James D. Hoefelmeyer Beilstein journal of organic chemistry. . 2016,第1期

机译：氯[8-（二甲磺酰基）喹啉-κN]铜的直接芳基化催化（I）
3. Coordination of ethylene to a zwitterionic Rh(III) half-sandwich complex: Influence of ambiphilic ligands on reactivity [J] . Boudreau J., Fontaine F.-G. Organometallics . 2011,第3期

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5. Synthesis of the Bifunctional Ambiphilic Molecule 2-(picolyl) trimethylstannane and Study of its Hydrolysis Kinetics Using Hydrogen NMR . [D] . Balasanthiran, Choumini. 2012

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6. Crystal structures of dichloridopalladium(II) -platinum(II) and -rhodium(III) complexes containing 8-(diphenylphosphanyl)quinoline [O] . Takayoshi Suzuki, Hiroshi Yamaguchi, Masayuki Fujiki, 2015

机译：含8-（二苯基苯基膦基）喹啉的二氯钯钯（II）铂（II）和铑（III）配合物的晶体结构
7. Coordination modes of the novel bifunctional nitrogen ligands 8-(2-pyridyl)quinoline and 8-(6-methyl-2-pyridy)quinoline towards palladium and platinum. X-ray structures of (8-(2-pyridyl)quinoline)Pd(Me)Cl, (8-(2-pyridyl)quinoline)Pd(C(O)Me)Cl and (8-(2-p2 [O] . Delis, J.G.P., Rep, M., Rulke, R.E., 1996

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8. Specific Oxidation of (Rh(CO)2Cl)2 by O2 via the Coordination of in Situ Generated HOOH. Implications for the RH(III)/Cu(II)-Catalyzed O2 Oxidation of 1-Alkenes to 2-Ketones [R] . Nyberg, E. D., Pribich, D. C., Drago, R. S. 1983

机译：O2（Rh（CO）2Cl）2通过原位生成的HOOH的配位氧化（Rh（CO）2Cl）2。 RH（III）/ Cu（II）催化氧化1-烯烃氧化成2-酮的意义

Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl) quinoline: Hydrolysis and Coordination to Cu~I, Ag~I and Pd~(II)

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