On the Redox Reactivity of a Geometrically Constrained Phosphorus(III) Compound.
On the Redox Reactivity of a Geometrically Constrained Phosphorus(III) Compound.
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DOI：
10.1002/chem.201703119
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发表时间：
2017-11
期刊：
影响因子：
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通讯作者：
T. Robinson;Daniel M. De Rosa;S. Aldridge;J. Goicoechea
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文献类型：
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作者：
T. Robinson;Daniel M. De Rosa;S. Aldridge;J. Goicoechea
研究了含N，N-二（3，5-二叔丁基-2-苯酚）酰胺钳形配体（P（ONO）; 1）的磷（III）配合物对氧化剂和还原剂的反应性.该化合物可以容易地氧化成磷（V）二卤代衍生物P（ONO）X2，其中X=Cl（2）、Br（3）和I（4）。通过氧化1分离类似的二氟化物的尝试是不成功的，仅产生氢氟化物P（ONO）（H）F（5），然而P（ONO）F2（6）可以通过2与KF的卤化物交换反应获得。化合物2可用作通过使用强刘易斯碱的氯离子置换的新型阳离子物质的前体。因此，2与2或3摩尔当量的二甲基氨基吡啶（DMAP）反应得到[P（ONO）（Cl）（DMAP）2 ]+（7）和[P（ONO）（DMAP）3 ]2+（8）。2与较弱的双齿碱2，2 '-联吡啶（bipy）反应得到[P（ONO）（Cl）（bipy）]+（9），尽管这种物质只有在加入卤化物提取剂后才可获得。双阳离子三（吡啶）加合物[P（ONO）（py）3 ]2+（10）也可通过4与吡啶的反应获得。使用氧气对1的氧化缓慢进行，并允许观察到两种化合物，混合价态二聚磷（III）/磷（V）化合物[P（ONO）（μ2 -O）（μ2：κ1，κ2 -ONO）P]（11）和完全氧化的物质[P（ONO）（μ2 -O）（μ2：κ1，κ2 -ONO）P（O）]（12）。最后，1与KC 8的反应导致推定的自由基阴离子[P（ONO）]的二聚化。通过形成P-P键得到[P（ONO）]22-（13）。与克里思的反应导致形成三角双锥物种P（ONO）（克里思）2（14）。
The reactivity of a geometrically constrained phosphorus(III) complex bearing the N,N-bis(3,5-di-tert-butyl-2-phenolate)amide pincer ligand (P(ONO); 1) towards oxidants and reductants is explored. This compound can be readily oxidized to the phosphorus(V) dihalo-derivatives P(ONO)X2 where X=Cl (2), Br (3) and I (4). Attempts at isolating the analogous difluoride through oxidation of 1 were unsuccessful yielding only the hydrofluoride P(ONO)(H)F (5), however P(ONO)F2 (6) can be accessed via a halide exchange reaction of 2 with KF. Compound 2 can be employed as a precursor to novel cationic species through chloride ion displacement using strong Lewis bases. Thus, reaction of 2 with two or three molar equivalents of dimethylaminopyridine (DMAP) affords [P(ONO)(Cl)(DMAP)2 ]+ (7) and [P(ONO)(DMAP)3 ]2+ (8). Reaction of 2 with the weaker bidentate base 2,2'-bipyridine (bipy) affords [P(ONO)(Cl)(bipy)]+ (9), although this species was only accessible upon addition of a halide abstracting agent. The dicationic tris(pyridine) adduct [P(ONO)(py)3 ]2+ (10) is also accessible by reaction of 4 with pyridine. Oxidation of 1 using oxygen gas proceeds slowly and allows for the observation of two compounds, a mixed valence dimeric phosphorus(III)/phosphorus(V) compound [P(ONO)(μ2 -O)(μ2 :κ1 ,κ2 -ONO)P] (11) and the fully oxidized species [P(ONO)(μ2 -O)(μ2 :κ1 ,κ2 -ONO)P(O)] (12). Finally, reaction of 1 using KC8 results in the dimerization of the putative radical anion [P(ONO)].- through formation of a P-P bond to afford [P(ONO)]22- (13). Reactions with TEMPO result in the formation of the trigonal bipyramidal species P(ONO)(TEMPO)2 (14).