Gallen Albert, Orgué Sílvia, Muller Guillermo, Escudero-Adán Eduardo C, Riera Antoni, Verdaguer Xavier, Grabulosa Arnald
Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès, 1-11, E-08028, Barcelona, Spain.
Dalton Trans. 2018 Apr 17;47(15):5366-5379. doi: 10.1039/c8dt00897c.
Both enantiomers of the optically pure Secondary Phosphine Oxide (SPO) t-BuMeP(O)H (1) have been obtained by deboronation of phosphinous acid-borane t-BuMeP(O)H·BH3 (3) with HBF4 followed by hydrolysis of the intermediate adduct t-BuMeP(O)H·BF3 (1·BF3), which has been isolated and crystallographically characterised. Complexes [MCl(COD)(κP-(R)-1)] (M = Ir, Rh; 4 and 7 respectively) have been detected in solution but could not be isolated while trans-[RhCl(CO)(κP-(S)-1)2] (9) has been successfully obtained in good yield. Gold complex [AuCl(κP-(S)-1)] (10) has been prepared and its crystal structure shows the presence of aurophilic interactions. Three new ruthenium complexes ([RuCl2(η6-p-cymene)(κP-(R)-1)], 12), ([RuCl2(CO)3(κO-(S)-1)], 13) and trans-([RuCl2(CO)2(κP-(S)-1)2], 14) have been synthesised and fully characterised, including the crystal structure of 12. Four palladium coordination compounds have been prepared: trans-[PdCl2(κP-(S)-1)2] (trans-15), [Pd(μ-Cl)(κP-(S)-1)2]2 (16·OH and 16·BF2) and [Pd(μ-OAc)(κP-(S)-1)2] (17) and the crystal structure of complex 16·OH proves the pseudobidentate coordination of the two molecules of 1. Three organometallic allylpalladium complexes have been prepared namely [Pd(η3-Ph2C2H3)Cl(κP-(S)-1)] (18) and [Pd(η3-Ph2C2H3)(κP-(S)-1)2] (19·OH and 19·BF2). The crystal structure of 19·BF2 constitutes the first allylpalladium-SPO complex reported to date.
通过用HBF₄对次膦酸硼烷t-BuMeP(O)H·BH₃（3）进行脱硼反应，随后水解中间体加合物t-BuMeP(O)H·BF₃（1·BF₃），已获得光学纯的二级氧化膦（SPO）t-BuMeP(O)H（1）的两种对映体，该中间体加合物已被分离并通过晶体学进行了表征。在溶液中检测到了配合物[MCl(COD)(κP-(R)-1)]（M = Ir、Rh；分别为4和7），但无法分离，而反式-[RhCl(CO)(κP-(S)-1)₂]（9）已成功以良好产率获得。制备了金配合物[AuCl(κP-(S)-1)]（10），其晶体结构显示存在亲金相互作用。合成并全面表征了三种新的钌配合物（[RuCl₂(η⁶-p-异丙基苯)(κP-(R)-1)]，12）、（[RuCl₂(CO)₃(κO-(S)-1)]，13）和反式-（[RuCl₂(CO)₂(κP-(S)-1)₂]，14），包括12的晶体结构。制备了四种钯配位化合物：反式-[PdCl₂(κP-(S)-1)₂]（反式-15）、[Pd(μ-Cl)(κP-(S)-1)₂]₂（16·OH和16·BF₂）以及[Pd(μ-OAc)(κP-(S)-1)₂]（17），配合物16·OH的晶体结构证明了两个1分子的假双齿配位。制备了三种有机金属烯丙基钯配合物，即[Pd(η³-Ph₂C₂H₃)Cl(κP-(S)-1)]（18）和[Pd(η³-Ph₂C₂H₃)(κP-(S)-1)₂]（19·OH和19·BF₂）。19·BF₂的晶体结构是迄今为止报道的首个烯丙基钯-SPO配合物。
