Two Triazole-Based Phosphine Ligands Prepared via Temperature-Mediated Li/H Exchange: CuI and AuI Complexes and Structural Studies

The kinetically favored
triazole-based phosphine 1-(2-(diphenylphosphino)­phenyl)-4-phenyl-1H-1,2,3-triazole (2, L1) and its
thermodynamically preferred isomer, 5-(diphenylphosphino)-1,4-diphenyl-1H-1,2,3-triazole (3, L2), were obtained
by the temperature-controlled lithiation of 2-bromotriazole followed
by the reaction with chlorodiphenylphosphine. The structures of phosphines 2 and 3 were determined by X-ray diffraction.
Upon reaction with late transition-metal derivatives (CuI, AgI, and AuI), phosphines 2 and 3 form complexes with monodentate (CuI, AgI, and AuI; κ1-P), chelate (CuI; κ2-P,N), bridged bidentate (CuI; μ2-P,N), and tridentate (CuI; μ2,κ2-P,N,N) modes of coordination. Reactions
with copper­(I) halides produced mono-, di-, and tetranuclear complexes, whereas the reaction of 2 with [Cu­(NCCH3)4]­BF4 yielded
the binuclear complex [Cu2(CH3CN)2{o-Ph2P­(C6H4)­{1,2,3-N3C­(Ph)­C­(H)}-μ-(κ-P,κ-N),κ-N}2]­(BF4)2 (10) with the ligand acting as a six-electron
donor involving phosphorus and two triazole nitrogen atoms. The copper
complexes of 2 and 3 containing rhomboid
Cu2X2 units, [(Cu)2(μ-X)2{o-Ph2P­(C6H4)­{1,2,3-N3C­(Ph)­C­(H)}-κ-P}2] (4, X = Cl; 5, X = Br), on treatment
with 1,10-phenanthroline and 2,2′-bipyridine gave mixed-ligand
complexes of the type [(CuX)­(N∩N-κ2-N,N)­{o-Ph2P­(C6H4)­{1,2,3-N3C­(Ph)­C­(H)}-κ-P}] (N∩N = 1,10-phen and 2,2′-bipy; X = Cl,
Br, and I).

通过温度控制锂化2-溴三唑，随后与氯二苯基膦反应，成功获得了动力学优势的磷化物1-(2-(二苯基膦基)苯基)-4-苯基-1H-1,2,3-三唑（2，L1）及其热力学上更易形成的异构体5-(二苯基膦基)-1,4-二苯基-1H-1,2,3-三唑（3，L2）。通过X射线衍射技术确定了磷化物2和3的结构。与后过渡金属衍生物（CuI、AgI和AuI）反应时，磷化物2和3形成了单齿配位（CuI、AgI和AuI；κ1-P）、螯合配位（CuI；κ2-P,N）、桥连双齿配位（CuI；μ2-P,N）和三齿配位（CuI；μ2,κ2-P,N,N）的复杂结构。与铜（I）卤化物反应产生了单核、双核和四核复合物，而2与[Cu(NCCH3)4]BF4反应则生成了双核复合物[Cu2(CH3CN)2{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(H)}-μ-(κ-P,κ-N),κ-N}2](BF4)2（10），其中配体作为涉及磷和两个三唑氮原子的六电子供体。含有菱形Cu2X2单元的2和3的铜复合物[(Cu)2(μ-X)2{o-Ph2P(C6H4){1,2,3-N3C(Ph)C(H)}-κ-P}2]（4，X = Cl；5，X = Br），经1,10-菲罗啉和2,2′-联吡啶处理，产生了具有混合配体的复合物[(CuX)(N∩N-κ2-N,N){o-Ph2P(C6H4){1,2,3-N3C(Ph)C(H)}-κ-P}]（N∩N = 1,10-phen和2,2′-bipy；X = Cl，Br和I）。