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Mono‐Phosphazenyl Phosphines (R2N)3P=N–P(NR2)2 – Strong P‐Bases, P‐Donors, and P‐Nucleophiles for the Construction of Chelates
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.1 ) Pub Date : 2020-05-27 , DOI: 10.1002/zaac.202000108 Julius F. Kögel 1 , Sebastian Ullrich 1 , Borislav Kovačević 2 , Sebastian Wagner 1 , Jörg Sundermeyer 1
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.1 ) Pub Date : 2020-05-27 , DOI: 10.1002/zaac.202000108 Julius F. Kögel 1 , Sebastian Ullrich 1 , Borislav Kovačević 2 , Sebastian Wagner 1 , Jörg Sundermeyer 1
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We present a convenient three‐step synthesis of amino substituted phosphazenyl phosphines of the general formula (R2N)3P=N–P(NR2)2 [NR2 = N(CH2)4, N(CH2)5, N(CH2)6]. These easily accessible mixed valent compounds display a surprisingly high proton affinity and basicity in the same range as the corresponding Schwesinger diphosphazene (Me2N)3P=N–P=NEt(NMe2)2 (Et‐P2) and Verkade's proazaphosphatrane superbases. Within the central [PIII–N=PV] scaffold, the phosphine PIII and not the phosphazene NIII atom is the center of highest proton affinity, basicity and donor strength. As P‐bases, the title compounds display calculated proton affinities between 265.8 (NR2 = NMe2) and 274.7 kcal·mol–1 [NR2 = N(CH2)4] and pKBH+ values between 26.4 (NR2 = NMe2) and 31.5 [NR2 = N(CH2)4] on the acetonitrile scale. As P‐nucleophiles, they are key intermediates in the synthesis of hyperbasic bis(diphosphazene) proton sponges, chiral bis(diphosphazene) proton pincers, bisphosphazides, and superbasic P2‐bisylides. Their Staudinger reactions as nucleophile towards 1,8‐diazidonaphthalene leading to 1,8‐naphthalene‐bisphosphazides is described in detail. The donor strength of the title compounds towards fragments [Se] and [Ni(CO)3] is in the same range as that of N‐heterocyclic carbenes.
中文翻译：
单膦烯基膦（R2N）3P = N–P（NR2）2 –用于螯合物构建的强P碱，P受体和P亲核试剂
我们提出了通式（R 2 N）3 P = N–P（NR 2）2 [NR 2 = N（CH 2）4，N（CH 2）5的氨基取代的磷腈基膦的便捷三步合成方法，N（CH 2）6 ]。这些容易获得的混合价化合物在与相应的Schwesinger二磷腈（Me 2 N）3 P = N–P = NEt（NMe 2）2（Et-P 2）和Verkade的proazaphosphatrane超级碱基。在中心的[P III –N = P V ]支架中，膦P III而不是磷腈N III原子是质子亲和性，碱度和供体强度最高的中心。作为P-碱，标题化合物的计算出的质子亲和力在265.8（NR 2 = NMe 2）和274.7 kcal · mol –1 [NR 2 = N（CH 2）4 ]之间，p K BH +值在26.4（NR 2 = NMe 2）和31.5 [NR 2 = N（CH 2）4 ]在乙腈刻度上。作为P-亲核试剂，它们是高碱性双（diphosphazene）质子海绵，手性双（diphosphazene）质子钳，双磷叠氮化物和超碱性P 2-二烷基化物合成的关键中间体。详细描述了它们作为1,8-二叠氮萘的亲核试剂导致1,8-萘-双磷叠氮的Staudinger反应。标题化合物对片段[Se]和[Ni（CO）3 ]的供体强度与N-杂环卡宾的范围相同。
更新日期：2020-05-27
中文翻译：
单膦烯基膦（R2N）3P = N–P（NR2）2 –用于螯合物构建的强P碱，P受体和P亲核试剂
我们提出了通式（R 2 N）3 P = N–P（NR 2）2 [NR 2 = N（CH 2）4，N（CH 2）5的氨基取代的磷腈基膦的便捷三步合成方法，N（CH 2）6 ]。这些容易获得的混合价化合物在与相应的Schwesinger二磷腈（Me 2 N）3 P = N–P = NEt（NMe 2）2（Et-P 2）和Verkade的proazaphosphatrane超级碱基。在中心的[P III –N = P V ]支架中，膦P III而不是磷腈N III原子是质子亲和性，碱度和供体强度最高的中心。作为P-碱，标题化合物的计算出的质子亲和力在265.8（NR 2 = NMe 2）和274.7 kcal · mol –1 [NR 2 = N（CH 2）4 ]之间，p K BH +值在26.4（NR 2 = NMe 2）和31.5 [NR 2 = N（CH 2）4 ]在乙腈刻度上。作为P-亲核试剂，它们是高碱性双（diphosphazene）质子海绵，手性双（diphosphazene）质子钳，双磷叠氮化物和超碱性P 2-二烷基化物合成的关键中间体。详细描述了它们作为1,8-二叠氮萘的亲核试剂导致1,8-萘-双磷叠氮的Staudinger反应。标题化合物对片段[Se]和[Ni（CO）3 ]的供体强度与N-杂环卡宾的范围相同。
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