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Integration of lead‐halide perovskite quantum dots (PQDs) into full‐color microarrays presents numerous advantages for full‐color micro‐LED displays. There is an urgent requirement for a new design approach that simplifies the creation of durable PQD/polymer composites to produce stable PQD microarrays. Here, mono‐2‐(methacryloyloxy)ethyl succinate (MMeS) is utilized as a functional ligand to synthesize green MMeS‐modified CsPbBr3 PQDs (M‐CPB PQDs). The subsequent photopolymerization of M‐CPB PQDs with 1,6‐hexanediol diacrylate (HDDA) forms a CsPbBr3 PQD/polymer composite. This composite exhibits a solid‐state photoluminescence quantum yield of 73.1%, and the photoluminescence intensity retains 72% of its original value after 17 days of continuous immersion in water. Stable green PQD/polymer microarrays can be printed using an ink containing M‐CPB PQDs, HDDA, diphenyl (2,4,6‐trimethylbenzoyl) phosphine oxide, and n‐dodecane via electrohydrodynamic jet printing and in situ polymerization under UV light irradiation. Full‐color patterns can also be generated with MMeS‐modified red, green, and blue PQDs. These findings highlight the critical role of functionalizing the surface ligands of PQDs to improve their processability, thereby facilitating the development of stable PQD/polymer microarrays. [ABSTRACT FROM AUTHOR]

A rigid pentadentate chelating ligand (H2L) has been utilized to synthesize a series of octacoordinate mononuclear complexes, [Dy(L)(Ph3PO)(OOCR)] (where R = C6H5 (1), C(CH3)3 (2), CF3 (3)) and a dinuclear complex, [Dy2(L)2(Ph3PO)2{(OOC)2C6H4}] (4) based on the highly anisotropic Dy(III) ion. All the complexes were structurally characterized by single-crystal X-ray diffraction studies. The complexes were formed by the coordination action of the dianionic pentadentate ligand [L]2−, one phosphine oxide, and carboxylate ligands. DC and AC magnetic measurements were performed on 1–4. Complexes 1–4 show SMM behaviour, under zero DC field for 1 and 4, and under 500 Oe and 1000 Oe DC fields for 2 and 3 respectively, with thermally activated, Raman, and Raman and quantum tunnelling dominant relaxation mechanisms for 1 and 2, 3 and 4, respectively. [ABSTRACT FROM AUTHOR]

A series of bis‐cyclometalated chiral‐at‐metal iridium(III) complexes containing a coordinated secondary phosphine oxide (SPO) have been synthesized and evaluated as catalysts in the asymmetric transfer hydrogenation (ATH) of acetophenone. The catalytic results show that SPO ligands have a non‐innocent role in activating the catalytic process. Additionally, it has been observed that for the same chiral descriptor (Δ‐at‐Ir or Λ‐at‐Ir), the major enantiomer formed depends on the nature of the cyclometalating ligand. These enantiodivergent results contravene the general assumption that the chiral‐at‐metal core‘s chirality dictates the sense of the chiral induction. A combined analysis of the main structural features of the catalysts deduced from XRD structures and in situ NMR spectroscopy allowed us to propose a simplified catalytic cycle and a working hypothesis to explain the observed enantioselectivities. [ABSTRACT FROM AUTHOR]

Epimers of the (1,10-phenanthroline-2,9-diyl)bis(ethyl(phenyl)phosphine oxide) (Et-Ph-BPPhen) ligand with two chiral centers (R,R/S,S and R,S) were synthesized. The configurational effects on the coordination ability and mechanism between these epimeric ligands and uranyl ions were thoroughly investigated. This work is helpful to reveal the effects of different conformations of epimeric ligands on their coordination properties. [ABSTRACT FROM AUTHOR]

Herein, we developed the recyclable ligand‐free iridium (Ir)‐hydride based Ir0 nanoparticles (NPs) for the first regioselective partial hydrogenation of PV‐substituted naphthalenes. Both the isolated and in situ generated NPs are catalytically active. A control nuclear magnetic resonance (NMR) study revealed the presence of metal‐surface‐bound hydrides, most likely formed from Ir0 species. A control NMR study confirmed that hexafluoroisopropanol as a solvent was accountable for substrate activation via hydrogen bonding. High‐resolution transmission electron microscopy of the catalyst supports the formation of ultrasmall NPs, and X‐ray photoelectron spectroscopy confirmed the dominance of Ir0 in the NPs. The catalytic activity of NPs is broad as showcased by highly regioselective aromatic ring reduction in various phosphine oxides or phosphonates. The study also showcased a novel pathway toward preparing bis(diphenylphosphino)‐5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐binaphthyl (H8‐BINAP) and its derivatives without losing enantioselectivity during catalytic events. [ABSTRACT FROM AUTHOR]

The two triple-armed species tris(2-carboxyethyl)nitromethane (H3tcenm) and tris(2-carboxyethyl)phosphine (H3tcep) have been used to synthesize seven uranyl ion complexes under (solvo)-hydrothermal conditions and in the presence of various structure-directing cations. The three carboxylate groups chelate three different cations and the nitro group is uncoordinated in [H2NMe2][UO2(tcenm)]·3H2O (1), [C(NH2)3][UO2(tcenm)]·0.5H2O (2) and [PPh3Me][UO2(tcenm)] (3), which crystallize as diperiodic coordination polymers with the hcb topology and minor variations in shape depending on the counterion. The two isomorphous complexes [UO2(tcenm)M(bipy)2][UO2(tcenm)]·3H2O, with M = Ni (4) or Cu (5) and bipy = 2,2′-bipyridine, display the same arrangement, with a M(bipy)22+ group bridging two adjoining carboxylate donors in one uranyl equatorial plane. [(UO2)2(tcenm)2Cu(R,S-Me6cyclam)]·2H2O (6), where R,S-Me6cyclam = 7(R),14(S)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, is the only triperiodic framework in the series, with the tcs topology resulting from CuII pillaring diperiodic, uranyl-based sql networks. H3tcep is oxidized in situ to give the phosphine oxide H3tcepo, which is partially deprotonated in [UO2(Htcepo)] (7); the phosphine oxide and the two carboxylate groups are coordinated, and the diperiodic, three-dimensional network formed has the point symbol {66} and the vertex symbol 62·62·63·66·64·64, with the rings involved in Hopf links formation. Only complexes 3 and 7 are significantly emissive in the solid state, with photoluminescence quantum yields of 9%, and the emission maxima positions are in agreement with the number of uranyl equatorial donors. [ABSTRACT FROM AUTHOR]

The reaction of 1,3,5-tris(diphenylphosphinylbenzene (L) with MnI2 in the presence of CuI (wet MeCN, 25°C, 30 min) leads to the formation of the complex [MnL4(H2O)2][Cu5I7(CH3CN)]·7MeCN with yield of 72%. The Mn2+ ion of this complex has a distorted Mn@O6 octahedral environment formed by four L ligands and two coordinated water molecules. The [Cu5I7(CH3CN)]2– anion has an unprecedented structure of the {Cu5I7} framework, which contains five copper atoms bound by bridging iodide ions (µ2, µ3, and µ4), and also four short Cu···Cu contacts (<2.80 Å). It has been shown that the synthesized complex at 298 K exhibits weak photoluminescence attributed to cluster-centered phosphorescence from the iodocuprate anion. [ABSTRACT FROM AUTHOR]

Phosphine oxides and spirocyclic compounds are privileged molecules widely employed in a variety of catalytic transformations either as chiral ligands for metals or bifunctional organocatalysts. Herein, we developed a Pd‐catalysed cross‐coupling reaction to synthesize spirocyclic amino‐phosphine oxides with a P‐stereogenic centre which could serve as potential P*(O), N‐ligands or organocatalysis. [ABSTRACT FROM AUTHOR]

A Cu/CPA co‐catalytic system has been developed for achieving the direct hydrophosphinylation of alkynes with phosphine oxides in delivering novel axially chiral phosphorus‐containing alkenes in high yields and excellent enantioselectivities (up to 99 % yield and 99 % ee). DFT calculations were performed to elucidate the reaction pathway and the origin of enantiocontrol. This streamlined and modular methodology establishes a new platform for the design and application of new axially chiral styrene‐phosphine ligands. [ABSTRACT FROM AUTHOR]

By the interaction of CuI with bis(2-pyridyl)phosphine oxides (2-Py)2RP(O) containing E-1-phenyl-2-aroylethenyl–C(Ph)=CHC(O)R′ (R′ = Ph, 2-thienyl) substituents, [Cu2I2L2] complexes are synthesized. Their structures are based on the rhomboidal Cu2I2 moiety whose copper atoms are N,N′-chelated by the indicated ligands. At room temperature, the crystalline samples of these complexes exhibit dark red photoluminescence (λmax = 680-685 nm) with a charge transfer from the Cu2I2 moiety to the ligand. [ABSTRACT FROM AUTHOR]

The treatment of nuclear spent fuels, especially the separation of minor actinides, is an imperative task for the healthy development of the nuclear industry. Up to now, it still remains a worldwide challenge to separate trivalent An3+ from Ln3+ because of their similar chemical properties. Therefore, investigating the mechanism behind the selective extraction of An3+ by theoretical methods is necessary. In this work, three phosphine oxide ligands with the same side structures but different bridging frameworks, Ph2PyPO, Ph2BipyPO and Ph2PhenPO, were investigated theoretically, and compared with each other using relativistic density functional theory. The results of QTAIM and MBO suggest that the Am--N bonds in the studied complexes have more covalent character than those in the Eu--N bonds, whereas the PDOS analysis indicates that more overlap exists between Am-5f and the Ph2PyPO's N-2p orbital than between Am-5f and Ph2BipyPO's N-2p, and Am-5f and Ph2PhenPO's N-2p orbital. However, the studied ligands all possess stronger affinities towards Am3+ than Eu3+, which partly results in the Am3+ selectivity towards Eu3+ in these three ligands. The calculated reaction free energy can reproduce the Am/Eu separation ability difference of three ligands well. This work offers some useful information for An/Ln separation of phosphine oxide ligands, and may help to design more efficient An3+/Ln3+ separation ligands. [ABSTRACT FROM AUTHOR]

The spent nuclear fuel has radioactive species such as actinides and lanthanides which hamper its reprocessing. This issue is undertaken by designing suitable organic ligands to strip off actinides from lanthanides. Due to the versatility of phenanthroline‐derived N, O‐donor ligands, we have looked into the electronic structure of N,O‐hybrid 1,10‐phenanthroline derived phosphine oxide ligands with various cyclic substitutions. The complexation behavior of these ligands with Am(III) and Eu(III) is evaluated using density functional theory calculations. Electronic structures divulge that in all these tetra‐coordinated complexes, the oxygen atoms bind strongly than the nitrogen atoms. The substitution of a benzene ring on the phosphorus increases the selectivity whereas the binding is enhanced by the substitution of cyclopentane. QTAIM analysis portrays the weak C−H−O interactions present in these complexes. Energy decomposition analysis in gas and solvent phases estimates the weak stabilizing interactions in these complexes. All the calculations bring out the salient structural features of these ligands which will further enrich our understanding of the tailoring of ligands for efficient uptake of Am (III) ions over Eu (III) ions. [ABSTRACT FROM AUTHOR]

The ring-opening polymerization (ROP) of cyclic esters provides access to biodegradable polymers with materials properties that can be tailored through appropriate catalyst design. Introduction of neutral donor ligands has emerged as an attractive opportunity to tune catalyst performance in a rational, inexpensive, and operationally simple manner; however, broader application of these ligands has been limited by our mechanistic-level understanding of these additives. In this perspective, we highlight the versatile roles of neutral donor ligands in modulating catalyst performance in the ROP of cyclic esters, and identify several unifying concepts and trends that emerge across a diverse range of catalyst systems (group I, II, XII–XIV, and the rare-earths (group III and the lanthanides)), neutral donor ligands (ethers, crown-ethers, amines, guanidines, carbenes, phosphines, and phosphine-oxides), and cyclic esters (ε-caprolactone, lactide, β-lactones). Shared learnings in design strategies, bonding preferences, and mechanisms of action help solidify relationships between catalyst structure and function, and illuminate promising future directions to leverage these effects in the synthesis of sustainable polymers. [ABSTRACT FROM AUTHOR]

The distinguishing feature of α-cationic phosphines is the presence of at least one substituent, normally (hetero)cyclic and positively charged, which is directly attached to the phosphorus atom. As result from this unique substitution pattern, the thus designed ligands depict significantly diminished donor properties if compared with their neutral counterparts. Thus, if in a hypothetical catalytic cycle, the step that determines the rate is facilitated by an increase of the electrophilicity at the metal center; then, the use of α-cationic ancillary phosphines can be highly beneficial. This fact, combined with their easy syntheses and stability, which allows an easy handling, make α-cationic phosphines a useful tool for the synthetic practitioner. Our research on the topic demonstrates that generally a remarkable ligand acceleration effect is observed when α-cationic phosphines are employed in Au(I)- and Pt(II)-promoted cycloisomerizations; moreover, in some cases even otherwise not operative transformations can be promoted. This Account describes how we entered into the topic, our efforts, and those of others to understand the coordination behavior of α-cationic phosphines and further develop their range of applications in catalysis; but it also identifies the drawbacks associated with their use, which limit their range of application. 1 Introduction 2 Polycationic Phosphines: Stronger Acceptors than Phosphites 3 Inconveniences Derived from the Use of (Poly)cationic phosphines 4 A Second Generation of Cationic Ligands: α-Pyridiniophosphines 5 Chiral α-Cationic Phosphines 6 α-Radical Phosphines and (Poly)cationic Phosphine Oxides 7 Conclusions and Outlook [ABSTRACT FROM AUTHOR]

Main observation and conclusion: Some 4‐hydroxy‐picolinic acid derived amides were revealed as more efficient ligands for Cu‐catalyzed coupling of (hetero)aryl halides with secondary phosphine oxides and phosphites. Only 3—5 mol% CuI and ligands were required to ensure coupling with a number of (hetero)aryl bromides and iodides to complete at 120 oC in 10—20 h. [ABSTRACT FROM AUTHOR]

Main observation and conclusion: Some 4‐hydroxy‐picolinic acid derived amides were revealed as more efficient ligands for Cu‐catalyzed coupling of (hetero)aryl halides with secondary phosphine oxides and phosphites. Only 3—5 mol% CuI and ligands were required to ensure coupling with a number of (hetero)aryl bromides and iodides to complete at 120 oC in 10—20 h. [ABSTRACT FROM AUTHOR]

The 2,6‐difluorophenyltrialkylstannanes 2,6‐F2C6H3SnR3 (1, R=Me; 2, R=Bu) were prepared from commercial products. With Ph2PLi, 1 and 2 underwent nucleophilic substitution to give the 2,6‐bis(diphenylphosphino)phenyltrialkylstannanes 2,6‐(Ph2P)2C6H3SnR3 (3, R=Me; 4, R=Bu). The reaction of 3 with n‐BuLi and BrCH2CH2Br afforded 2,6‐bis(diphenylphosphino)bromobenzene (2,6‐(Ph2P)2C6H3Br, 5), the oxidation of which gave the related bis(phosphine oxide) 2,6‐[Ph2P(O)]2C6H3Br (6). The reaction of 5 with n‐BuLi gave rise to the formation of 2,6‐bis(diphenylphosphino)phenyl lithium, 2,6‐(Ph2P)2C6H3Li (7). Attempts to prepare the related bis(phosphine oxide) 2,6‐[Ph2P(O)]2C6H3Li (8) from 6 in a similar way at low temperatures was hampered by decomposition. Compounds 3, 5 and 7 hold potential for a new anionic tridentate PCP−coordinating ligand, namely, the bis(2,6‐diphenyl)phosphinophenyl ion [2,6‐(Ph2P)2C6H3]−. [ABSTRACT FROM AUTHOR]

Tris[2-(3′-cyanopropoxy)phenyl]phosphine oxide has been obtained via the alkylation of tris(2hydroxyphenyl)phosphine oxide with 4-bromobutyronitrile in the presence of K2CO3. The product structure has been elucidated by means of X-ray diffraction analysis. The terminal cyano groups in the obtained phosphine oxide have been converted into tetrazole rings via the click-reaction with NH4N3 to give a new hybrid tripodal propeller ligand, tris{2-[3′-(tetrazol-5′′-yl)propoxy]phenyl}phosphine oxide. Palladium(II) complexes of the prepared ligand and its short-linker analog, tris[2-(tetrazol-5′-ylmethoxy)phenyl]phosphine oxide, have been synthesized. Cytotoxicity of the ligands and their Pd(II) complexes has been studied. [ABSTRACT FROM AUTHOR]

We report herein a new family of carbene ligands based on an indolizine‐ylidene (Indolizy) moiety. The corresponding gold(I) complexes are easily obtained from the gold(I)‐promoted cyclization of allenylpyridine precursors. Evaluation of the electronic properties by experimental methods and also by DFT calculations confirms strong σ‐donating and π‐accepting properties of these ligands. Cationization of the gold(I) complexes generates catalytic species that trigger diverse reactions of (poly)unsaturated precursors. When armed with a methylene phosphine oxide moiety on the stereogenic center adjacent to the nitrogen atom, the corresponding bifunctional carbene ligands give rise to highly enantioselective heterocyclizations. DFT calculations brought some rationalization and highlighted the critical roles played by the phosphine oxide group and the tosylate anion in the asymmetric cyclization of γ‐allenols. [ABSTRACT FROM AUTHOR]

Six centrosymmetric mononuclear Eu3+ and Tb3+ complexes of the type [LnL2(hfac)3] have been synthesized employing diphenyl(pyridin-2-yl)phosphine oxide (Ph2P(O)Py), diphenyl(pyridimin-2-yl)phosphine oxide (Ph2P(O)Pym), and diphenyl(pyrazin-2-yl)phosphine oxide (Ph2P(O)Pyr) as supporting ligands (L). The complexes [LnL2(hfac)3] (L = Ph2P(O)Py and Ph2P(O)Pyr) comprise an eight-coordinate Ln3+ ion with two monodentate O-donor phosphine oxides and three bidentate hfac− anions. In the [Ln{Ph2P(O)Pym}2(hfac)3] complexes, the Ln3+ ion is nine-coordinated by three bidentate hfac− anions and two Ph2P(O)Pym ligands, one of which is bound to Ln in a N,O-bidentate chelating mode, and the other acts as a monodentate O-donor ligand. The complexes display bright solid-state photoluminescence with emission quantum yields up to 56%. The integral intensity of 5D0 → 7F2 transition in the emission spectra of the Eu(III) complexes strongly depends on the coordination environment of the Eu3+ ion. The asymmetric coordination geometry around Eu3+ results in the large radiative rate constants. The crystals of the Eu(III) and Tb(III) complexes exhibit triboluminescence upon breaking under ambient conditions. The relationship between the triboluminescent properties and crystal structures of the complexes is discussed. [ABSTRACT FROM AUTHOR]

Three new Ru complexes with N-P(OH)-N donor ligands were synthesized and characterized. A ruthenium complex with a ligand with quinolinyl side arms exhibited monodentate coordination through the phosphorus atom with an intramolecular POH···N(quinolinyl) hydrogen bond but with no interaction between nitrogen donors and the ruthenium center. Two pentamethylcyclopentadienyl ruthenium complexes with a ligand with pyridyl side arms exhibited fac-k3-NPN' tridentate coordination to the metal center, one with an interionic POH···FPF5 hydrogen bond in the crystal. A paramagnetic nickel [Ni3(N-P(O)-N)4] cluster was also characterized; the crystal structure shows three nickel centers in two different environments. The central nickel is coordinated to four deprotonated ligands, two are bidentate k²-NO, two are monodentate k-O and is connected to the other two nickel centers by two sets of bridging µ²-O,P moieties. Non-central nickel centers are each coordinated to one bidentate ligand k²-PN and one monodentate ligand k-P. [ABSTRACT FROM AUTHOR]

Two new phosphine oxide‐functionalized 1,10‐phenanthroline ligands, tetradentate 2,9‐bis(butylphenylphosphine oxide)‐1,10‐phenanthroline (BuPh‐BPPhen, L1) and tridentate 2‐(butylphenylphosphine oxide)‐1,10‐phenanthroline (BuPh‐MPPhen, L2), were synthesized and studied comparatively for their coordination with trivalent actinides and lanthanides. The complexation mechanisms of these two ligands toward trivalent f‐block elements were thoroughly elucidated by NMR spectroscopy, UV/vis spectrophotometry, fluorescence spectrometry, single‐crystal X‐ray diffraction, solvent extraction, and theoretical calculation methods. NMR titration results demonstrated that 1 : 1 and 1 : 2 (metal to ligand) lanthanides complexes formed for L1, whereas 1 : 1, 1 : 2 and 1 : 3 lanthanide complexes formed for L2 in methanol. The formation of these species was validated by fluorescence spectrometry, and the corresponding stability constants for the complexes of NdIII with L1 and L2 were determined by using UV/vis spectrophotometry. Structures of the 10‐coordinated 1 : 1‐type complexes of EuL1(NO3)3 and [EuL2(NO3)3(H2O)] Et2O in the solid state were characterized by X‐ray crystallography. In solvent‐extraction experiments, L1 exhibited extremely strong extraction ability for both AmIII and EuIII, whereas L2 showed nearly no extraction toward AmIII or EuIII due to its high hydrophilicity. Finally, the structures and bonding natures of the complex species formed between AmIII/EuIII and L1/L2 were analyzed in DFT calculations. [ABSTRACT FROM AUTHOR]

Two potentially tripodal ligands, tris(1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)phosphine oxide (OP(1,2,3Tz1−Ph)3) and tris(1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)phosphine oxide (OP(1,2,3Tz1−benz)3), were used in reactions with [Re(CO)5Br] and (NEt4)2[Tc(CO)3Cl3]. While the formation of rhenium complexes with bidentate and tridentate coordinated phosphine oxides was observed, for technetium only cationic complexes with tripodal coordinated OP(1,2,3Tz1−R) ligands were isolated. The products have been characterized spectroscopically and by single crystal X‐ray diffraction. [ABSTRACT FROM AUTHOR]

New tripodal ligand, tris(2-carbamoylmethoxyphenyl)phosphine oxide, has been synthesized via the alkylation of tris(2-hydroxyphenyl)phosphine oxide with chloroacetamide. The ligand structure has been studied by means of IR and NMR (1H, 31P) spectroscopy as well as X-ray diffraction. [ABSTRACT FROM AUTHOR]

We report thermodynamic, geometric, and electronic parameters for the interaction between neutral ligands and the [Hg(H2O)]2+ dication, using the B3LYP/6–311 + G(d,p) approach. Gibbs free energies for the interaction were employed to rank the affinity order of the several neutral ligands. To identify the parameters that characterize the affinity between the two fragments, the metal-ligand interaction was analyzed according to the EDA, NBO, and QTAIM decomposition schemes. The phosphine oxide showed the highest affinity for the Hg(H2O)2+ dication, mainly due to the P=O bond polarization. Ligands containing the sulfur atom, characterized by a high covalent component for the metal-ligand interaction, are the following in the interaction order. According to the Gibbs free energy for substitution of one water molecule in the [Hg(H2O)2]2+ complex, the sequence for the affinity order is: phosphine oxide > thioketone > thioesther > lactam > amide > amine > carboxylic acid > thiophene > ketone > esther > thiol > thiocyanate > ammonia > disulfide > aldehyde > ether > haloydrin > alcohol > enol > azide. [ABSTRACT FROM AUTHOR]

A combination of experimental (SQUID magnetometry) and quantum‐chemical (BS‐DFT, CASSCF(n,m)/NEVPT2, DDCI3) methods is used to probe the influence of terminal ligands on magnetic exchange coupling in the series of [Cu2(μ2‐OAc)4L2] complexes with O‐donor terminal ligands extended by two novel complexes containing phosphine oxide ligands. The possibilities and limitations of these approaches are discussed. The influence of terminal ligands on magnetic superexchange interaction was quantified by two contributions—the first contribution is associated with structural changes within the {Cu(μ2‐OAc)4Cu} core, while the second contribution is due to the difference in the electronic influence of different terminal ligands at a given core geometry. Both contributions were found to be approximately of the same order of magnitude. These results indicate that magnetic exchange coupling, known to be highly sensitive to the distortions in core geometry, is not solely determined by the core structure. Our findings are consistent with the fact that various one‐ and multiparameter magnetostructural correlations reported in the literature have only a qualitative predictive capability. [ABSTRACT FROM AUTHOR]

First examples of luminescent MnII thiocyanate complexes are presented. A series of such compounds has been synthesized via the reaction of Mn(NCS)2 with bis(phosphine oxides), Ph2P(O)–X–(O)PPh2, where X = CH2 (L1), CH2CH2 (L2), CH2CH2CH2 (L3), CH2C(=CH2)CH2 (L4), C(=CH2)C(=CH2) (L5) and C≡C (L6). The L1, L3 and L4 ligands, when reacted with Mn(NCS)2 on air (EtOH/acetone, r.t.), produce chelate complexes [MnII(O^O)2(NCS)2]. Under similar conditions, L5 gives ionic complex [MnII(L5)3][MnII(NCS)4], whereas L6 affords chain coordination polymer (CP) [MnII(L6)2(NCS)2]n. By contrast, ligand L2 results in formation of mixed‐valent chain CP [MnIIMnIII(L2)3(NCS)5]n. Complex [Mn(L4)2(NCS)2] and CP [Mn(L6)2(NCS)2]n display unique dual luminescence, i.e. the intraligand fluorescence (blue band) and MnII‐centered phosphorescence (red band), the ratio of which is largely modulated by excitation wavelength. Through this feature, the luminescence color of these complexes can be smoothly tuned from deep‐blue to red. Complex [Mn(L5)3][Mn(NCS)4] shows MnII‐based phosphorescence only. [ABSTRACT FROM AUTHOR]

As a result of the implementation of two approaches, the Pudovik reaction (the reaction of macrocyclic azomethines with secondary phosphine oxides) and the Kabachnik–Fields reaction (three-component one-pot process involving dialdehydes, diamines, and secondary phosphine oxides), novel N,O-containing macrocyclic ligands with phosphine oxide groups were first obtained. The synthesized macrocycles are a kind of α-aminophosphoryl compounds that can be used in the synthesis of supramolecular systems. [ABSTRACT FROM AUTHOR]

• Chiral zinc amidate catalyzes additions of Et 2 Zn to aldehydes in high yields and mediocre ee. • Carboxamides bearing a phosphine oxide group work as bifunctional ligands. • Spiro[indane-1,2′-pyrrolidin]-5′-one constitutes a rigid backbone for effective chiral ligands. A series of bifunctional spiro ligands bearing "carboxamide–phosphine oxide" groups and ethylzinc carboxamidates from these ligands as catalysts for Et 2 Zn additions to aldehydes were reported. Excellent yields were obtained with moderate ee′s in Et 2 Zn additions to benzaldehyde derivatives, implying effectiveness of our newly designed catalytic structures as well as mediocre stereocontrol by these chiral ligands. Possible transition states were suggested based on the crystal structures of two ligands. [ABSTRACT FROM AUTHOR]

The synthesis of complexes of TaOCl 3 and TaSCl 3 with pyridyl and phosphine oxide ligands are reported and spectroscopic and structural data compared. The white complexes, [TaOCl 3 (OPPh 3) 2 ], [TaOCl 3 (L-L)] (L-L = 1,10-phenanthroline, 2,2′-bipyridyl, Ph 2 P(O)CH 2 P(O)Ph 2 , Ph 2 P(O)CH 2 CH 2 P(O)Ph 2 and o -C 6 H 4 (P(O)Ph 2) 2), have been prepared from TaCl 5 , O(SiMe 3) 2 and the ligands in anhydrous CH 2 Cl 2 solution. The corresponding yellow [TaSCl 3 (OPPh 3) 2 ] and [TaSCl 3 (L-L)] were made similarly using S(SiMe 3) 2. The complexes have been characterised by microanalysis, IR and NMR (1H, 31P{1H}) spectroscopy. X-ray crystal structures have been obtained for [TaOCl 3 (1,10-phen)], [TaSCl 3 (1,10-phen)], [TaOCl 3 { o -C 6 H 4 (P(O)Ph 2) 2 }], [TaSCl 3 (OPPh 3) 2 ], [TaSCl 3 {Ph 2 P(O)CH 2 CH 2 P(O)Ph 2 }] and [TaSCl 3 (MeCN) 2 ], which all contain mer -chlorines and with the neutral ligands trans to O/Cl or S/Cl. The structure of the Ta(V) dimer [Cl 2 S(1,10-phen)Ta(µ-O)Ta(1,10-phen)SCl 2 ], formed by trace hydrolysis, is also reported. Comparisons between the complexes of TaOCl 3 and TaSCl 3 and their niobium analogues are discussed. [ABSTRACT FROM AUTHOR]

Two isostructural mononuclear CoII complexes, [Co(xantpo)(NCE)2] (E=S (1) and O (2); xantpo=9,9‐dimethyl‐4,5‐bis(diphenylphosphoryl) xanthene), supported by a bidentate phosphine oxide ligand are reported. The cobalt complexes exhibit characteristic tetrahedral structures coordinated with two oxygen and two nitrogen atoms. Magnetic property measurements show their similar static magnetic behaviours but very different dynamic magnetic behaviours. Both complexes show field‐induced slow magnetic relaxation behaviours, but the relaxation of 2 is much slower than that of 1. Fittings to the magnetic data and ab initio CASSCF calculations reveal significant changes in the zero field splitting (ZFS) parameters (D and E), which can be attributed to the small geometrical changes of the Co ions and the different ligand field strength of the two terminal ligands. [ABSTRACT FROM AUTHOR]

Six metal–organic frameworks with the combination of a novel tripodal ligand tris[4-(1H-imidazol-1-yl)phenyl]phosphine oxide (tipo) and different polycarboxylates, namely [Zn2(bpdc)2(tipo)(H2O)]·5H2O (1), [Cd(tipo)2][Cd2(bdc)3]·4H2O (2), [Cd2(ndc)2(tipo)2]·3H2O (3), [Cd2(bpedc)2(tipo)2]·15H2O (4), [Cd2(hfdc)2(tipo)2]·10H2O (5) and [Ni2(tipo)2(bpedc)(H2O)4]·2NO3·2DMF (6), were synthesized and structurally characterized. Compound 1 featured a 2D → 3D parallel polycatenation of a 3,3,4-connected net with an unusual 4 degrees of catenation and an index of separation of 2. Compound 2 showed an unprecedented polycatenation of charged networks 2D kgd and 3D pcu constructed by different organic ligands. Compound 3 exhibited a combination of a 2D → 3D parallel polycatenation of the sql net and polythreading. Compound 4 featured a 4-fold interpenetration of a 3,5-connected 3,5T1 net. Compound 5 displayed an unusual 2-fold interpenetration of the sdd net. Compound 6 presented a 2-fold interpenetration of the 3,4-connected bey net with a cationic framework. The luminescence properties of 1–5 in the solid state were investigated. Also, compound 6 showed a tendency for rapid selective dye capture and highly efficient Cr2O72− removal from aqueous solution. [ABSTRACT FROM AUTHOR]

A luminescent TbIII complex with a hexafluoroacetylacetone (hfa) ligand shows a characteristic back energy transfer (BEnT), which leads to high temperature sensitivity and potential application as a thermosensitive paint. Ligand‐assisted BEnT was observed when a phosphine oxide ligand was introduced into Tb(hfa)3 complex, which was shown to affect the activation energy (ΔEa) and frequency factor (A) in the BEnT process between TbIII ion and hfa ligands. According to temperature‐dependent emission‐lifetime measurements of mononuclear Tb(hfa)3 complexes with monodentate phosphine oxides and polynuclear Tb(hfa)3 complexes with bidentate phosphine oxides, the ΔEa and A values of polynuclear TbIII complexes were smaller than those of mononuclear TbIII complexes. Phosphorescence spectra and lifetimes of each Gd(hfa)3 complex revealed that excited states of hfa ligands in TbIIIcomplexes differed from those of the polynuclear TbIII complexes and mononuclear TbIII complexes. The differences in the ΔEa and A values between polynuclear and mononuclear TbIII complexes were caused by the formation of different excited states, such as delocalization of the excited state in the polynuclear TbIII complexes and localization of excited states in the mononuclear TbIII complexes. In particular, small ΔEa and A values of polynuclear TbIII complexes provided high, effective activation of the BEnT at low temperature, which resulted in high‐sensitive temperature‐dependent phosphor materials over a wide temperature range. Thermosensitive materials: The introduction of various phosphine oxide ligands into luminescent Tb(hfa)3 complexes leads to control of the activation energy and frequency factor in the ligand‐assisted back energy transfer process, and this results in improved tunability of the thermosensing property of the complex (see picture). [ABSTRACT FROM AUTHOR]

A simple and efficient access to a new P‐chiral, but so far racemic ligand class featuring ortho‐trityl and ortho‐biaryl motifs is reported. The phosphines are prepared by efficient three‐ to four‐step modular syntheses from simple branched alkyl(diphenyl)phosphine oxides in 52–63% overall yield. They form stable gold complexes, which were characterized by X‐ray crystallography and spectroscopic methods. Fundamental catalytic properties of the complexes were studied in 1,6‐enyne cycloisomerization reactions of achiral substrates to benchmark their activity against the efficient achiral catalyst (JohnPhos)AuCl. The results show that the new complexes can be applied in amounts down to 100 ppm allowing the cycloisomerization reactions to be performed with turnover frequencies of 20000 h−1 and turnover numbers of up to 10000 h−1. [ABSTRACT FROM AUTHOR]

Keywords: Hydrogenation; Iridium; Ligands; Nanoparticles; Phosphine Oxides EN Hydrogenation Iridium Ligands Nanoparticles Phosphine Oxides 1 1 1 09/20/23 20230925 NES 230925 B Heterogeneous and recyclable b ligand-free nanoparticles of iridium(0) enabled highly selective hydrogenation of distal unsubstituted aromatic rings to generate novel phosphine ligands. Hydrogenation, Iridium, Ligands, Nanoparticles, Phosphine Oxides Back Cover: Ligand-Free Ultrasmall Recyclable Iridium(0) Nanoparticles for Regioselective Aromatic Hydrogenation of Phosphine Oxide Scaffolds: An Easy Access to New Phosphine Ligands (Angew. [Extracted from the article]

Hydrogenation, Iridium, Ligands, Nanoparticles, Phosphine Oxides The iridium-hydride species and hydrogen bonding between the substrate and solvent facilitate the catalysis, as reported by Fabrice Gallou, Sachin Handa et al. in their Research Article (e202307139). Keywords: Hydrogenation; Iridium; Ligands; Nanoparticles; Phosphine Oxides EN Hydrogenation Iridium Ligands Nanoparticles Phosphine Oxides 1 1 1 09/20/23 20230925 NES 230925 B Heterogeneous and recyclable b ligand-free nanoparticles of iridium(0) enabled highly selective hydrogenation of distal unsubstituted aromatic rings to generate novel phosphine ligands. [Extracted from the article]

• Investigating the effects of diphosphine ligands on the anticancer behavior of cycloplatinated(II) complexes of 2,2´-Bipyridine N Oxide. • Cytotoxic activity evaluation of the cycloplatinated(II) complexes gainst human lung (A549), ovarian (SKOV3), breast (MCF-7) cancer cell lines as well as normal breast (MCF-10A) cell line. • DNA binding interaction studies of cycloplatinated(II) complexes using comet assay, EMSA, and molecular docking. A substantial amount of attention has been paid to chemical research on cyclometalated platinum compounds that contain diphosphine ligands due to their coordination behavior and reactivity. To introduce new anticancer metallodrugs, a series of synthesized mononuclear and dinuclear cycloplatinated(II) complexes derived from deprotonated 2,2´-bipyridine N-oxide (bipyO) bearing 1,1′-bis(diphenylphosphino)alkanes (alkane: methane (dppm), ethane (dppe) and propane (dppp)) were biologically evaluated to probe the effect of diphosphine ligands on their anticancer behavior. The antitumor effects of (1a, 1b, 1c, 2a, 2b, and 2c) were evaluated against human lung (A549), ovarian (SKOV3), breast (MCF-7) cancer cell lines as well as normal breast (MCF-10A) cell line. The interactions of complexes with DNA structures (PDB IDs: 1BNA, and 1LU5) as term of binding modes and binding sites were determined using molecular docking. Compound [Pt(p -tolyl)(κ 2 N,C - bipyO)(κ 2 P -dppe)], 1b, inhibited cell proliferation significantly more effectively than cisplatin and exhibited significantly greater in vitro cytotoxicity against A549, SKOV3, and MCF7 cell lines. Complexes [Pt(p -tolyl)(κ 2 N,C - bipyO)(κ 2 P -dppp)], 1c and [Pt 2 (p -tolyl) 2 (κ 2 N,C - bipyO) 2 (µ 2 P -dppe)], 2b also displayed stronger cytotoxic activity than cisplatin on SKOV3, and MCF7 cancer cell lines. In evaluating cytotoxic effects on MCF-10A cells, all compounds showed low toxicities with higher selectivity index than cisplatin. EMSA, and Comet assay showed that 1b, can intercalate with DNA and targets the genomes of cancerous cells. The apoptosis assay of 1b on MCF-7 cancer cells showed that by increasing the concentration of this compound from 1 to 3 and then 5 µM, the percentage of cells entering the apoptotic stage increases from about 9.4% to 61.39% and then to 74.10%. Based upon the biological analyses, the alkyl linker chain length in 1,1′-bis(diphenylphosphino)alkanes appear to be a key factor controlling the biological activity. Interestingly, cloplatinated(II) complexes bearing 1,1′-bis(diphenylphosphino)ethane (dppe), revealed promising anticancer potentials, which makes them be good candidates for future studies in the cancer treatment field. [Display omitted] [ABSTRACT FROM AUTHOR]

The geometries of a series of lanthanide complexes with phosphine oxide-type ligands (either mono- or polydentate) were optimized using the PM6/Sparkle semiempirical computational approach. The activation barriers of coordination reactions (i.e. the conversion of a complex with κ1-bound ligand into a complex with multiply bound one) were estimated. The κ2-chelate formation with a pyridine-2,6-diylbis(diphenylphosphine oxide) ligand is favorable only for a few largest lanthanides, while κ1-coordination is the most probable case for the smaller ones. [ABSTRACT FROM AUTHOR]

A series of precursors of novel tripodal ligands (2-XCH2CH2CH2OC6H4)3PO, where X = AcO, HO, MeSO2O, Br, N3, were synthesized by the alkylation of the starting tris(2-hydroxyphenyl)phosphine oxide with 3-bromopropyl acetate followed by hydrolysis of the resulting triacetate to triol and conversion of the latter to trimesylate. Treratment of the resulting trimesylate with LiBr or NaN3 was used to prepare the corresponding tribromo or triazido derivatives. [ABSTRACT FROM AUTHOR]

This paper reports the synthesis and characterization of a number of monocyclic systems with one or two phosphorus atoms in the scaffold. The cyclic systems with one Patom are: 1-phosphacyclodeca-3,8-diyne, 1-phosphacycloundeca- 3,9-diyne, 1-phosphacyclododeca-3,10-diyne, 1-phosphacyclotrideca- 3,11-diyne, 1-phosphacyclotetradeca-3,12-diynerings were further stabilized by phenyl- or 2,4,6-tri-tert-butylphenyl rings as third ligand and sulfur or oxygen atoms as fourth ligand. The rings with two P-atoms are 1,8-diphosphacyclotetradeca- 4,11-diyne and 1,10-diphosphacyclooctadeca- 5,14-diyne, with phenyl rings and oxygen at the P-centers. For many of the products the structures and conformations in the solid state were obtained by X-ray studies. [ABSTRACT FROM AUTHOR]

A ligand system containing three carbamoyl moieties secured onto a triphenylphosphine oxide platform (2-R 2 NC(O)CH 2 OC 6 H 4 ) 3 PO, where R = Me ( 1 ), Bu ( 2 ), and cyclo -Hex ( 3 ) has been developed for lanthanide complexation and extraction from aqueous solutions. The influence of non-coordinating alkyl substituents at the nitrogen atoms in the carbamoyl side arms on coordination and extraction properties of tripodal ligands 1 – 3 was studied. Two new ligands 1 and 3 with alkyl substituents of different bulkiness were synthesized and characterized by spectroscopic methods. Single-crystal X-ray structures have been determined for ligands 1 and 2 . The selected coordination chemistry of ligands 1 – 3 with Ln(NO 3 ) 3 (Ln = La, Nd, Lu) has been evaluated. The 1:1 complexes of all ligands 1 – 3 were synthesized and characterized via elemental analysis and IR spectroscopy; in addition, the crystal structure of the ligand 1 complex with neodymium nitrate was determined by X-ray diffraction. Solution structure of 1:1 complexes was examined by IR and multinuclear ( 1 H, 13 C, and 31 P) NMR spectroscopy. A formation of 1:2 complexes with lanthanum and lutetium nitrates (IR, NMR, ESI-MS ) has been examined and structure of the major components of 1:2 complexes solutions has been suggested for ligands 1 – 3 . Preliminary extraction studies of Ln(III) (Ln = La, Nd, Eu, Lu) from 3 M NH 4 NO 3 into 1,2-dichloroethane show that ligands 2 and 3 recover lanthanides much better than their mono analog [2-(Bu 2 NC(O)CH 2 O)-5-Et-C 6 H 3 ]P(O)Ph 2 and known extractant Ph 2 P(O)CH 2 C(O)NBu 2 . [ABSTRACT FROM AUTHOR]

Recently, all-inorganic cesium lead halide (CsPbX3, X = Cl, Br, and I) nanocrystals (NCs) have drawn wide attention because of their excellent optoelectronic properties and potential applications. However, one of the most significant challenges of such NCs is their low stability against protonic solvents. In this work, we demonstrate that by incorporating a highly branched capping ligand, trioctylphosphine oxide (TOPO), into the traditional oleic acid/oleylamine system, monodisperse CsPbX3 NCs with excellent optoelectronic properties can be achieved at elevated temperatures (up to 260 °C). The size of such NCs can be varied in a relatively wide range. The capping of TOPO on NCs has been verified through Fourier transform infrared spectroscopy measurement. More importantly, the presence of TOPO can dramatically improve the stability of CsPbX3 NCs against ethanol treatment. After ethanol treatment for 100 min, the emission intensity of the TOPO-capped sample dropped only 5%, whereas that of non-TOPO-capped NCs dropped up to 86%. This work may shed some light on the preparation and application of CsPbX3 NCs with higher stability. [ABSTRACT FROM AUTHOR]

A number of precursors of new tripodal ligands was obtained by hydroxyethylation of the starting tris(2-hydroxyphenyl)phosphine oxide, followed by conversion of the resulting tris[2-(2-hydroxyethoxy) phenyl]phosphine oxide to trimesylate. The treatment of the latter with LiBr or NaN3 afforded the corresponding tribromo and triazido derivatives. [ABSTRACT FROM AUTHOR]

[Display omitted] • M-O bonds were found to be stronger than M-N bonds whereas the M-S bonds were found to be stronger than M-N bonds. • PO ligands have slight excess covalent character (0.5%) in M-O/N bonds. • Phenanthroline based PS ligand is the best bet for extraction of Am3+ ions from Eu3+. • The Am-S/N/O bonds were stronger than the Eu-S/N/O bonds. Spent nuclear fuel management, particularly the separation of minor actinides, is critical to the continued growth of the nuclear industry and to address the global energy crisis. However, due to the identical chemical properties of trivalent An3+ and Ln3+, it is difficult to distinguish them. Therefore, theoretical research on the mechanism of selective extraction of An3+ is needed. Two phosphine oxide ligands and two phosphine sulphide ligands with similar structures but different bridging frameworks namely phenanthroline and biphenyl, were theoretically explored and compared using relativistic density functional theory in the solvent phase. Here, the M-O bonds are stronger than the M-S bonds. QTAIM shows that the M-O/N bonds of the phosphine oxide ligands have a small amount of covalent character. Gibbs free energy shows that the formation of the complexes is spontaneous while energy decomposition analysis deciphers the binding of M(NO 3) 3 to these ligands. All the ligands studied had greater affinity for Am3+ than for Eu3+, which contributes to the selectivity of Am3+ over Eu3+ in the water medium. This study provides some important information for the An/Ln separation of phosphine oxide and phosphine sulphide ligands, which may help in the development of more effective phosphine based ligands for the separation of An3+/Ln3+ ions. [ABSTRACT FROM AUTHOR]

Extraction behavior of some selected actinides like U(VI), Th(IV), and Am(III) was investigated with three different H-phosphine oxides, viz. diphenyl hydrogen phosphine oxide (DPhPO), dihexyl hydrogen phosphine oxide (DHePO) and diphenyl phosphite (DPP). The H-phosphine oxides exhibited a dual nature towards the extraction of actinides where the ligand not only extracts the metals by cation exchange but also by coordination with the phosphoryl group at lower and higher acidic concentrations, respectively. Among all ligands employed, DPhPO showed highest extraction with actinides with a substituent dependent trend as follows: DPhPO > DHePO > DPP. This trend emphasizes the importance of substituents around the phosphine oxide towards their extraction of actinides. The coordination behavior of DPhPO was studied by investigating its corresponding complexes with Th(NO3)4 and UO2(NO3)2. The metal complexes of these actinides were characterized using FT-IR, 1H and 31P NMR spectroscopic techniques. Density Functional Theory (DFT) calculations were also performed to understand the electronic and geometric structure of the ligand and the corresponding metal complexes. [ABSTRACT FROM AUTHOR]

Chiral organophosphorus compounds possessing a P-stereogenic center have been widely used as agricultural chemicals, pharmaceuticals, organocatalysts, and ligands for transition-metal catalysis. P-Stereogenic intermediates bearing a tert-butyl(methyl)phosphino group are important for the preparation of several commonly used diphosphine ligands. However, previously reported synthetic methods used hazardous starting materials and are difficult to operate. In order to overcome these limitations, a new and convenient synthesis for a number of P-stereogenic intermediates possessing a tert-butyl(methyl)phosphino group has been developed. The reported route relies on an air- and moisture-stable secondary phosphine oxide prepared from a readily available starting material, trichlorophosphane. [ABSTRACT FROM AUTHOR]

Inspired by the unique character of enzymes, we developed novel chiral SPO (secondary-phosphine-oxide) ligand (SPO-Wudaphos) which can enter into both ion pair and H-bond noncovalent interactions. The novel chiral SPO-Wudaphos exhibited excellent results in the asymmetric hydrogenation of α-methylene-γ-keto carboxylic acids, affording the chiral γ-keto acids with up to over 99 % ee. A series of control experiments and DFT calculations were conducted to illustrate the critical roles of both the ion pair and H-bond noncovalent interactions. [ABSTRACT FROM AUTHOR]

An unexpected substitution of the anionic chelating ligands at the MII centre by a neutral tripodal ligand has been observed in the reaction of MnII, CoII, NiII and CuII hexafluoroacetylacetonates (hfac) with tris(2-pyridyl)phosphine (Py3P) or its oxide (Py3P = O). The nature of the metal ion in M(hfac)2 and the M/L ratio determine the degree of substitution of hfac-anions (partial vs. total) and therefore, the structure of the complex formed (scorpionate vs. bis-scorpionate ones, respectively). Hence, the reaction of the ligands with [Cu(hfac)2(H2O)2] in an equimolar ratio affords scorpionate [Cu(N,N′,N′′-Py3P = X)(O,O′-hfac)(O-hfac)], wherein one hfac-ligand chelates metal, while the other hfac acts as an O-monodentate one. Using the two equivalents of Py3P in this reaction leads to [Cu(N,N′,N′′-Py3P)2](hfac)2, which contains a bis-scorpionate cation [Cu(Py3P)2]2+ and two noncoordinated hfac-anions. [Co(hfac)2(H2O)2] and [Ni(hfac)2(H2O)2], regardless of the M/L molar ratio, react with Py3P = O to give cationic scorpionates [M(N,N′,N′′-Py3P = O)(O,O′-hfac)(H2O)](hfac), in which one hfac-anion is noncoordinated. In contrast, [Mn(hfac)2(H2O)2], on interaction with Py3P, results in the cationic complex [Mn(N,N′,N′′-Py3P)2][Mn(hfac)3]2 bearing a bis-scorpionate cation [Mn(Py3P)2]2+ and two [Mn(hfac)3]2− counterions. The synthesized scorpionates have been characterized by X-ray diffractometry, cyclic voltammetry, SQUID magnetometry, FT-IR and UV-Vis techniques. [ABSTRACT FROM AUTHOR]

The effect of surfactant micelles and the second ligand on the efficiency of energy transfer in the Tb-flunixin complex was studied. The fluorescence intensity of the Tb-flunixin complex was shown to 100-fold increase in the presence of Tween 80 micelles and the second trioctylphosphine oxide ligand. A procedure for the fluorimetric determination of flunixin in the Flunex drug product (NITA-FARM, Saratov, Russia) was developed. The linearity range of the calibration curve was from 1 × 10 to 1 × 10 M, r = 0.991, and the limit of detection was 4 × 10 M (3σ). [ABSTRACT FROM AUTHOR]

New tridentate ether-phosphine {P, 2O} and ether-phosphine oxide {OP, 2O} ligands with P and O donor-atoms have been synthesized starting from ClCH 2 CH(OCH 3 ) 2 . The oxidation process of Ph 2 PCH 2 CH(OCH 3 ) 2 to its oxide derivative Ph 2 P( O)CH 2 CH(OCH 3 ) 2 was monitored by 31 P NMR for the first time. The desired ligands and their Co(II) complexes structures were deduced from IR, EA, MS, NMR, UV–Vis., TG/DTG and XRD physical measurements. The tridentate chelating coordination behavior of the ether-phosphine wasn't detected leading only to the mono-dentate coordination mode through the phosphorous atoms to set up a X 2 Co[η 1 -Ph 2 PCH 2 CH(OCH 3 ) 2 ] 2 as final isomer formula (X = Cl or Br). The Cl 2 Co[η 1 -Ph 2 PCH 2 CH(OCH 3 ) 2 ] 2 isomer belongs to complex 1 was supported by single crystal measurement. Polar/non-polar intermolecular short contacts were detected by XRD and Hirshfeld surface theoretical analysis. [ABSTRACT FROM AUTHOR]