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首页> 外文期刊>Chemistry: A European journal >eta(4)-HBCC-sigma,pi-Borataallyl Complexes of Ruthenium Comprising an Agostic Interaction
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eta(4)-HBCC-sigma,pi-Borataallyl Complexes of Ruthenium Comprising an Agostic Interaction

机译：eta（4）-HBCC-sigma，pi-硼酸烯丙基络合物的钌，具有农业相互作用

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摘要

Thermolysis of [Cp*Ru(PPh2(CH2)PPh2)BH2(L-2)] 1 (Cp*=eta(5)-C5Me5; L=C7H4NS2), with terminal alkynes led to the formation of eta(4)-sigma,pi-borataallyl complexes [Cp*Ru(mu-H) B{R-C=CH2}(L)(2)] (2a-c) and eta(2)-vinylborane complexes [Cp*Ru(R-C=CH2)BH(L)(2)] (3a-c) (2a, 3a: R=Ph; 2b, 3b: R=COOCH3; 2c, 3c: R=p-CH3-C6H4; L=C7H4NS2) through hydroboration reaction. Ruthenium and the HBCC unit of the vinylborane moiety in 2a-c are linked by a unique eta(4)-interaction. Conversions of 1 into 3a-c proceed through the formation of intermediates 2a-c. Furthermore, in an attempt to expand the library of these novel complexes, chemistry of s-borane complex [Cp*RuCO(mu-H)BH2L] 4 (L=C7H4NS2) was investigated with both internal and terminal alkynes. Interestingly, under photolytic conditions, 4 reacts with methyl propiolate to generate the eta(4)-sigma,pi-borataallyl complexes [Cp*Ru(mu-H)BH{R-C=CH2}(L)] 5 and [Cp*Ru(mu-H) BH{HC=CH-R}(L)] 6 (R=COOCH3; L=C7H4NS2) by Markovnikov and anti-Markovnikov hydroboration. In an extension, photolysis of 4 in the presence of dimethyl acetylenedicarboxylate yielded eta(4)-sigma,pi-borataallyl complex [Cp*Ru(mu-H) BH{R-C=CH-R}(L)] 7 (R=COOCH3; L=C(7)H(4)NS2). An agostic interaction was also found to be present in 2a-c and 5-7, which is rare among the borataallyl complexes. All the new compounds have been characterized in solution by IR, H-1, B-11, C-13 NMR spectroscopy, mass spectrometry and the structural types were unequivocally established by crystallographic analysis of 2b, 3a-c and 5-7. DFT calculations were performed to evaluate possible bonding and electronic structures of the new compounds.
机译：[Cp * Ru（PPh2（CH2）PPh2）BH2（L-2）] 1（Cp * = eta（5）-C5Me5; L = C7H4NS2）与末端炔烃的热解导致eta（4）- sigma，pi-硼烷基烯丙基络合物[Cp * Ru（mu-H）B {RC = CH2}（L）（2）]（2a-c）和eta（2）-乙烯基硼烷络合物[Cp * Ru（RC = CH2） BH（L）（2）]（3a-c）（2a，3a：R = Ph; 2b，3b：R = COOCH3; 2c，3c：R = p-CH3-C6H4; L = C7H4NS2）。钌和2a-c中乙烯基硼烷部分的HBCC单元通过独特的eta（4）相互作用连接。 1到3a-c的转化通过中间体2a-c的形成进行。此外，为了扩展这些新型配合物的文库，对内部和末端炔烃均研究了S-硼烷配合物[Cp * RuCO（mu-H）BH2L] 4（L = C7H4NS2）的化学性质。有趣的是，在光解条件下，4与丙酸甲酯反应生成eta（4）-sigma，pi-硼烷基烯丙基络合物[Cp * Ru（mu-H）BH {RC = CH2}（L）] 5和[Cp * Ru （mu-H）BH {HC = CH-R}（L）] 6（R = COOCH3; L = C7H4NS2）通过Markovnikov和反Markovnikov硼氢化。延伸地，在乙炔二甲酸二甲酯的存在下光解4产生eta（4）-sigma，pi-硼烷基烯丙基络合物[Cp * Ru（mu-H）BH {RC = CH-R}（L）] 7（R = COOCH 3; L ＝ C（7）H（4）NS2）。还发现在2a-c和5-7中存在异味相互作用，这在硼烷烯丙基配合物中很少见。所有新化合物均已在溶液中通过IR，H-1，B-11，C-13 NMR光谱，质谱进行了表征，并且通过2b，3a-c和5-7的晶体学分析明确确定了结构类型。进行了DFT计算，以评估新化合物的可能键合和电子结构。

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