Taube Clemens, Schwedtmann Kai, Noikham Medena, Somsook Ekasith, Hennersdorf Felix, Wolf Robert, Weigand Jan J
Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062, Dresden, Germany.
Department of Chemistry, Faculty of Science, Mahidol University, 272, Tungphayathai, Rama 6 Road, Rachathewi, Bangkok, 10400, Thailand.
Angew Chem Int Ed Engl. 2020 Feb 24;59(9):3585-3591. doi: 10.1002/anie.201911483. Epub 2019 Dec 30.
[L P((PhP) C H )][OTf] (4 a,b[OTf]) and [L P(PPh ) ][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl-substituted dipyrazolylphosphane triflate salts [L P(pyr) ][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; L =1,3-dialkyl-4,5-dimethylimidazol-2-yl; pyr=3,5-dimethylpyrazol-1-yl) with the secondary phosphanes PhP(H)C H P(H)Ph) and Ph PH. A stepwise double P-N/P-P bond metathesis to catena-tetraphosphane-2,3-diium triflate salt [(Ph P) (L P) ][OTf] (7 a[OTf] ) is observed when reacting 3 a[OTf] with diphosphane P Ph . The coordination ability of 5 b[OTf] was probed with selected coinage metal salts [Cu(CH CN) ]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph PPL )Au} ][OTf] (9[OTf] ) was unexpectedly formed as a result of a chloride-induced P-P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [(5 b)M(CH CN) ][OTf] (M=Cu, Ag) (10[OTf] , 11[OTf] ).
[L P((PhP)C H )][OTf]（4 a,b[OTf]）和[L P(PPh ) ][OTf]（5 b[OTf]）由咪唑鎓取代的双吡唑基膦三氟甲磺酸盐[L P(pyr) ][OTf]（3 a,b[OTf]；a：R = Me，b = iPr；L = 1,3 - 二烷基 - 4,5 - 二甲基咪唑 - 2 - 基；pyr = 3,5 - 二甲基吡唑 - 1 - 基）与仲膦PhP(H)C H P(H)Ph和Ph PH反应制备。当3 a[OTf]与双膦P Ph 反应时，观察到逐步的双P - N/P - P键复分解反应生成链状四膦 - 2,3 - 二鎓三氟甲磺酸盐[(Ph P) (L P) ][OTf]（7 a[OTf]）。用选定的碱金属盐[Cu(CH CN) ]OTf、AgOTf和AuCl(tht)（tht = 四氢噻吩）探究了5 b[OTf]的配位能力。对于AuCl(tht)，由于氯离子诱导的P - P键断裂，意外地形成了螺旋配合物[{(Ph PPL )Au} ][OTf]（9[OTf]）。弱配位的三氟甲磺酸根阴离子使得能够形成预期的铜(I)和银(I)配合物[(5 b)M(CH CN) ][OTf]（M = Cu，Ag）（10[OTf]，11[OTf]）。
