Structural diversity of copper(I) complexes formed by pyrrole- and dipyrrolylmethane-based diphosphine ligands with cu-X···HN hydrogen bonds.

Metal complexes containing hydrogen bond donor/acceptor groups are interesting because of their applications in several areas. In the course of our investigation on the synthesis of metal complexes using newly developed pyrrole-based diphosphine ligands, a few structurally interesting copper(I) complexes containing the pyrrolic NH hydrogen bond donors were synthesized. The reaction of 2,5-bis(diphenylphosphinomethyl)pyrrole (PNP) with an equimolar quantity of CuX (X = Cl, Br, and I) afforded the binuclear copper(I) complexes [Cu(µ-X)(µ-PNP-P,P)]2 (1-3) in very good yields (87-90%). Conversely, the analogous reaction between 1,9-bis(diphenylphosphinomethyl)diphenyldipyrrolylmethane (PNNP) and CuX (X = Cl, Br, and I) yielded the mononuclear Cu(I) complexes [CuX(PNNP-P,P)] (4-6) in very good yields (∼88%), in which the diphosphine ligand is chelated to the copper metal atom. Interestingly, when this reaction was carried out with a 1:2 mol ratio of ligand/metal, the cubane-like tetranuclear Cu(I) complex, [Cu4I4{µ-Ph2C(C4H3N)2-1,9-(CH2PPh2)2-P,P}2] 7, was isolated in 68% yield. In addition, the reaction between the dipyrrolyldiphosphine ligand (PNNP) and CuCl in the presence of 1 equiv of 1,10-phenanthroline monohydrate and NaBF4 afforded a novel ionic binuclear mixed-ligand Cu(I) complex, [Cu2(µ-X)(µ-PNNP-P,P)(NN)2]BF4 8, where NN = 1,10-phenanthroline in 57% yield. The structures of all these complexes were confirmed by the single-crystal X-ray diffraction method and are supported by spectroscopic data. In contrast to the PNP pincer ligand, the dipyrrolyl-diphosphine ligand (PNNP) adopts chelation as well as bridging coordination modes with Cu(I) atoms, indicating its flexibility of bonding. In all the structures, the Cu-X···HN type of hydrogen bonds involving the metal halide ion as acceptor and the pyrrolic NH as donor are present with the Cu-X···H angles, which deviate from the favored 90°, as observed in their solid state structures. Further, the presence of this type of hydrogen bond was confirmed by NBO, AIM, and Hirshfeld analyses.

Pyrrole-based new diphosphines: Pd and Ni complexes bearing the PNP pincer ligand.

A new class of diphosphine PNP pincer ligand, 2,5-bis(diphenylphosphinomethyl)pyrrole 2, was synthesized by the reaction between Ph2PH and 2,5-bis(dimethylaminomethyl)pyrrole in 90% yield. The analogous reaction of Ph2PH with 1,9-bis(dimethylaminomethyl)diphenyldipyrrolylmethane readily afforded a PNNP type diphosphine ligand, 1,9-bis(diphenylphosphinomethyl)diphenyldipyrrolylmethane 5 in 92% yield. These phosphine compounds were oxidized with H2O2 and S8 to give the corresponding phosphoryl and thiophosphoryl compounds 6-9 in very good yields. The reaction of the PNP pincer ligand 2 with [PdCl2(PhCN)2] in the presence of Et3N afforded the mononuclear Pd(II) complex, [PdCl{C4H2N-2,5-(CH2PPh2)2-κ(3)PNP}] 10 in 87% yield. Conversely, treatment of 2 with [PdCl2(PhCN)2] in the absence of Et3N gave the dinuclear Pd(II) complex [Pd2Cl4{µ-C4H3N-2,5-(CH2PPh2)2-κ(2)PP}2], the structure which is proposed based on the spectroscopic data. When 2 was treated with Pd(0) precursor [Pd2(dba)3]·CHCl3 the dinuclear Pd(I) complex [Pd2{µ-C4H2N-2,5-(CH2PPh2)2-κ(2)PN,κ(1)P}2], 12, was obtained in 23% yield. The formation of complex 12 is solvent dependent, which transforms into complex 10 in CDCl3 as studied by variable temperature (1)H and (31)P NMR methods. Treatment of 2 with [Ni(OAc)2]·4H2O gave the mononuclear Ni(II) pincer complex [Ni(OAc){C4H2N-2,5-(CH2PPh2)2-κ(3)PNP}], 13, which upon treatment with an excess of LiCl or LiBr or KI afforded the respective halide ion substituted Ni(II) complexes, [NiX{C4H2N-2,5-(CH2PPh2)2-κ(3)PNP}] (X = Cl, Br, and I), 14-16, in very good yields. The structures of 5, 2,5-bis(diphenylphosphorylmethyl)pyrrole 6, 10, 12, and 14-16 were determined by the single crystal X-ray diffraction method. In the structure of 12, two short contacts between the diagonally positioned Pd and P atoms are observed. To understand these weak interactions, density functional theory (DFT) calculations were done and an interaction MO diagram is presented.

Mononuclear, helical binuclear palladium and lithium complexes bearing a new pyrrole-based NNN-pincer ligand: fluxional property.

A new pyrrole based NNN-pincer ligand, 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole 2, was readily synthesized in two steps from pyrrole in 56% yield. The lithiation of the pincer ligand 2 using n-BuLi led to isolation of the dimeric lithium complex, [Li{µ-C(4)H(2)N-2,5-(CH(2)Me(2)pz)(2)-N,N,N}](2) 4, in 23% crystalline yield. The transmetalation reaction of 4 with [Pd(PhCN)(2)Cl(2)] afforded the mononuclear Pd(II) complex, [PdCl{C(4)H(2)N-2,5-(CH(2)Me(2)pz)(2)-N,N,N}] 5, containing one chloride ion in 45% yield. Alternatively 5 was obtained in an excellent yield of 87% by the reaction 2 of with [Pd(COD)Cl(2)] in the presence of triethylamine. On the contrary, a 20-membered macrometalacyclic molecule, [Pd(2)Cl(4){µ-C(4)H(3)N-2,5-(CH(2)Me(2)pz)(2)-N,N}(2)] 6, in which two PdCl(2) units are bridged by two molecules of 2 to give a helical structure, was synthesized by the reaction of 2 with [Pd(COD)Cl(2)] in the absence of base. The acetate analogue of complex 5, [Pd(OAc){C(4)H(2)N-2,5-(CH(2)Me(2)pz)(2)-N,N,N}] 3, was obtained by the treatment of 2 with [Pd(OAc)(2)]. The pyrrole twist angle of 5 is higher than that of 3. Complexes 3 and 5 show an AB pattern for their methylene protons at room temperature in CDCl(3) as well as in DMSO-d(6). The variable temperature NMR studies showed that the acetate and chloride complexes exhibit slightly different coalescence temperatures, which is a solvent dependent phenomenon, and twist angles.

Macrocyclic and acyclic molecules synthesized from dipyrrolylmethanes: receptors for anions.

A new class of macrocyclic and acyclic molecules was synthesized by the Mannich reactions of dipyrrolylmethanes to investigate anion recognition. The X-ray structures of the macrocycle and sulfate complexes are reported.