Chlorido[N,N′‐dibenzyl‐N′′‐(trichloroacetyl)phosphoramidato‐κ2O,O′](1,10‐phenanthroline‐κ2N,N′)copper(II)

In the title complex, [Cu(C₁₆H₁₆Cl₃N₃O₂P)Cl(C₁₂H₈N₂)], the Cu^II cation presents a square‐pyramidal environment, where the CuO₂N₂ base is formed by two O atoms from carbonyl and phosphoryl groups, and by two N atoms from a 1,10‐phenanthroline molecule. A coordinated Cl atom occupies the apex. N—H...Cl hydrogen bonds link the molecules into one‐dimensional chains. The trichloromethyl group is rotationally disordered over two positions, with occupancies of 0.747 (7) and 0.253 (7).     

Synthesis and investigations of mixed-ligand lanthanide complexes with N,N′-dipyrrolidine-N′′-trichloracetylphosphortriamide,dimethyl-N-trichloracetylamidophosphate, 1,10-phenanthroline and 2,2′-bipyrimidine

Coordination compounds with general formula [Ln(L¹)₃phen], where Ln = Nd, Eu, Er, Yb, HL¹ = N,N′-dipyrrolidine-N′′-trichloracetylphosphortriamide, phen = 1,10-phenanthroline; [Ln(L¹)₃bpm], where Ln = La, Nd, Eu, Gd, Er, Y, bpm = 2,2′-bipyrimidine and [{Ln(L²)₃}₂(μ-bpm)], where Ln = La, Nd, Eu, Gd, Er, Y, HL² = dimethyl-N-trichloracetylamidophosphate have been synthesized and characterized by means of IR and UV–Vis spectroscopy. Crystal structures of [Nd(L¹)₃phen] (1), [Nd(L¹)₃bpm] (2) and [{Nd(L²)₃}₂(μ-bpm)] (3) have been determined. It was found, that in the deprotonated form the phosphoryl ligands (L¹)^? and (L²)^? are coordinated to the neodymium atoms in a bidentate manner via the oxygen atoms of the phosphoryl and the carbonyl groups with formation of six-membered metallocycles. In the case of compounds 1 and 2 the 1,10-phenanthroline (or 2,2′-bipyrimidine) molecules are coordinated to the metals in a bidentate manner via the nitrogen atoms. In contrast 2,2′-bipyrimidine acts in the bidentate-bridge mode forming binuclear complex 3. Variable-temperature magnetic susceptibility measurements of 3 and [{Gd(L²)₃}₂(μ-bpm)] (4) reveal a weak antiferromagnetic interaction between the two magnetic centres, whereas in the case of [{Eu(L²)₃}₂(μ-bpm)] (5) the presence of spin–orbit coupling leads to a deviation from the Curie and Curie–Weiss laws.     

Photovoltaic Properties of Polymer Film Composites with a Tetranuclear Copper Complex Cu4L4(OCH3)4 (L− = N,N′-Dibenzyl-N″-Trichloroacetylphosphotriamide)

Theoretical and Experimental Chemistry - A study was carried out on the photovoltaic and photoconductive properties of film composites of a copolymer of styrene with nonyl methacrylate and...     

Novel heteroligand complexes of Co(II), Cu(II), Ni(II) and Mn(II) formed by 2,2′-dipyridyl or 1,10-phenanthroline and phosphortriamide ligands: Synthesis and structure

This paper presents examples of mixed-ligand Co(II), Cu(II), Ni(II) and Mn(II) complexes, with a distorted octahedral coordination geometry, with 2,2′-dipyridyl or 1,10-phenanthroline and phosphortriamide ligands. The complexes of the general type ML₂·Lig (where M = Co(II), Cu(II), Ni(II), Mn(II); L⁻ = {Cl₃C(O)NP(O)R₂}⁻ (R = NHBz, NHCH₂CHCH₂, NEt₂); Lig = 2,2′-dipyridyl or 1,10-phenanthroline) were synthesised and characterised by means of X-ray diffraction, IR and UV–Vis spectroscopy. The phosphortriamide ligands are coordinated via oxygen atoms of phosphoryl and carbonyl groups involved in six-membered metal cycles. The additional ligands 2,2′-dipyridyl or 1,10-phenanthroline are coordinated to the central atom, forming five-membered cycles.     

New carbacylamidophosphates (CAPh) and CAPh-containing coordination compounds: structural peculiarities

Structural Chemistry - The new carbacylamidophosphate derivative HL1 (1) with general formula Cl3CC(O)N(H)P(O)(CH2C5H4N)2 named...     

Varieties in structures of Co(II), Ni(II) and Cu(II) coordination compounds based on dimethyl pyridin-2-ylcarbamoylphosphoramidate

A series of new 3d metal complexes based on dimethyl pyridin-2-ylcarbamoylphosphoramidate (HL) was synthesized. The compounds with general formula M(HL)₂Cl₂·nH₂O and M(L)₂·nH₂O (M=Co²⁺, Cu²⁺, Ni²⁺) were characterized by means of single-crystal X-ray analysis and IR spectroscopy. The organic ligands in all complexes are coordinated via oxygen atom of the carbonyl group and nitrogen atom of the heterocycle. The coordination environment of the central atoms is a distorted octahedron. The axial positions in the Co(II) and Ni(II) complexes with deprotonated ligands are occupied by water molecules. The Co(II) and Cu(II) complexes with phosphoryl ligands in a neutral form have different ligands in the axial positions: in the Co(II) complex, the positions are occupied by two water molecules, whereas in the Cu(II) complex, the positions are occupied by two chlorine anions. The structure of HL was experimentally and theoretically obtained by utilizing single-crystal X-ray analysis and DFT calculations. The computationally optimized geometric parameters for HL show a good agreement with the experimental results.     

Dinuclear 3D metal complexes based on a carbacylamidophosphate ligand: redetermination of the ligand crystal structure

Dinuclear Ni(II), Co(II) and Zn(II) complexes of general formula $ \left[ {{\text{M}}_{ 2}^{\text{II}} {\text{Cl}}_{ 4} \left( {\text{HL}} \right)_{ 4} \left( {\text{i-PrOH}} \right)_{ 2} \cdot 2\left( {\text{i-PrOH}} \right)} \right] $ with a carbacylamidophosphate ligand, namely 2,2,2-trichloro-N-(dipiperidine-1-yl-phosphoryl)acetamide (CCl₃C(O)N(H)P(O)[N(CH₂)₅]₂), were synthesized and characterized by physicochemical and spectroscopic methods. Electronic absorption spectra of the nickel and cobalt complexes were measured at room temperature in toluene and in the solid state. The crystal structures of HL and [Ni₂Cl₄(HL)₄(i-PrOH)₂·2(i-PrOH)] have been determined by single-crystal XRD studies. Earlier, the structure of a monoclinic C2/c modification of HL was reported. In this paper, redetermination of the structure of HL with triclinic crystal system, P $ \overline{1} $ , was made. The nickel complex is a chloro-bridged dimer, in which the Ni(II) centers are in a distorted octahedral geometry and the neutral HL is coordinated via its phosphoryl oxygen atom. This coordination mode was determined for the first time for 3D metal carbacylamidophosphate complexes.