Phosphorus Donor Atoms Research Articles

Chemoselective Post-Synthesis Modification of Pyridyl-Substituted, Aromatic Phosphorus Heterocycles: Cationic Ligands for Coordination Chemistry.

Triazaphospholes are potential polydentate ligands due to the presence of both phosphorus and nitrogen donor atoms within the aromatic 5-membered heterocycle. The incorporation of an additional pyridyl-substituent opens up the possibility of a post-synthesis modification via chemoselective and also stepwise alkylation exclusively of the nitrogen atoms. This can be controlled by the choice and by the stoichiometry of the electrophile and allows the targeted synthesis of a variety of novel mono- and dicationic ligands. Reaction with Cu(I)-halides causes the formation of cuprates of the type [CuXn](n-1)-, which enables coordination of the π-acidic phosphorus donor to the negatively charged metal core, which is favored over the coordination by a strongly σ-donating nitrogen atom. The use of cationic triazaphosphole derivatives can be used as a strategy to enforce the coordination of the ligand to an electron rich metal solely via the phosphorus atom. However, there is a subtle balance between the formation of either coordination polymers or dimeric structures, as the substitution pattern on the heterocycle and the nature of the halide have a large influence on the coordination motifs formed.

The Synthesis of Novel P,N-Ferrocenylpyrrolidine-Containing Ligands and Their Application in Pd-Catalyzed Allylic Alkylation – A Synthetic and Mechanistic Investigation

AbstractThe synthesis of a series of planar chiral P,N-ferrocenylpyrrolidine-containing ligands, with varying substituents at the phosphorus donor atom, is described. The phosphorus donor atom was introduced via a diastereoselective ortho-directed metalation of N-methylpyrrolidinyl ferrocene followed by a quench with various chlorophosphines. These P,N systems are very active in Pd-catalyzed allylic alkylation of 1,3-diphenylpropenyl acetate with dimethylmalonate (conversions of up to 100%) and demonstrated good levels of enantioselectivity (up to 85% ees). Good selectivity for the (R)-enantiomer was observed and mechanistic studies, involving X-ray crystallography and NMR spectroscopic experiments, were employed to help rationalize the observed stereochemical outcome of the reaction.

Synthesis and Characterization of the New Cluster Complex {Mo3S4} with the Hemilabile Phosphine-Selenoether Ligand

The reaction of [Mo3S4(Tu)8(H2O)]Cl4·4H2O (Tu is thiourea) with (PhCH2CH2)2-PCH2CH2SeC5H11) (PSe) followed by purification on a chromatographic column packed with silica gel using a saturated solution of KPF6 in acetone as an eluent results in the formation of [Mo3S4Cl3(PSe)3]PF6 (I) in a yield of 44%. Compound I is characterized by X-ray diffraction analysis, 1H, 31P{1H}, and 77Se NMR spectroscopy, IR spectroscopy, UV-Vis spectroscopy, cyclic voltammetry, and electrospray ionization mass spectrometry. Several species differed in the coordination mode of three PSe ligands, which can bind to molybdenum via one (phosphorus) or two (phosphorus and selenium) donor atoms, are formed in a solution of compound I at room temperature. This behavior is not observed for the compounds similar in structure with PS ligands of an analogous type. Complex I demonstrates a higher catalytic activity than its analogue with the PS ligand in the reduction of nitrobenzene to aniline under the action of diphenylsilane.

Universal Quantum Computing Using Electronuclear Wavefunctions of Rare-Earth Ions

We propose a scheme for universal quantum computing based on Kramers rare-earth ions. Their nuclear spins in the presence of a Zeeman-split electronic crystal field ground state act as 'passive' qubits which store quantum information. The qubits can be activated optically by fast coherent transitions to excited crystal field states with a magnetic moment. The dipole interaction between these states is used to implement CNOT gates. We compare our proposal with a similar one based on phosphorus donor atoms in silicon and discuss the significantly improved CNOT gate time as compared to rare-earth implementations via the slower dipole blockade.

Palladium and Platinum Complexes Containing Diphenyl‐2‐(3‐methyl)indolylphosphine

Syntheses and characterisation of group ten complexes containing the ligand diphenyl‐2‐(3‐methyl)indolylphosphine are presented herein. The complexes [trans‐PdCl2{PPh2(C9H8N)}2] (1), [cis‐PtCl2{PPh2(C9H8N)}2] (2), [trans‐Pd(CH3)Cl{PPh2(C9H8N)}2] (3) and [trans‐Pt(CH3)Cl{PPh2(C9H8N)}2] (4) have all been structurally characterized by X‐ray crystallography. In all cases, the ligands coordinate to the metal centres via the phosphorus donor atom (κ1‐P) and the pendent NH groups on the indolyl rings of the ligand are orientated so that there is some degree of interaction with the metal–chloride bonds. The unexpected reactivity of 4 with Na[B{3,5‐C6H3(CF3)2}4] is also reported. In this case, the product resulting from this reaction was found to be [Pt{3,5‐C6H3(CF3)2}2{PPh2(C9H8N)}2].

Hydroamination reactions catalyzed by [Au2(μ-Cl)(μ-bis(phosphino)ferrocene)][BArF24

1,1′-bis(phosphino)ferrocene ligands are commonly employed in a variety of catalytic systems. These ligands are of particular interest as the steric and electronic properties of the phosphorus donor atoms can be altered by changing the substituents of the phosphines. In addition, the ferrocene backbone of the ligands provides unique electronic and conformational flexibility to these ligands. Previous investigations in this lab have examined catalytic ring closing reactions using a series of gold compounds with bis(phosphino)ferrocene ligands, [Au2Cl2(μ-PP)]. These gold compounds were shown to react with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Na[BArF24], to generate a cationic species with the general formula [Au2(μ-Cl)(μ-PP)][BArF24] that are much more efficient catalysts than the [Au2Cl2(μ-PP)] compounds. In this study, a series of [Au2Cl2(μ-PP)] (μ-PP = 1,1′-bis(diphenylphosphino)ferrocene (dppf), 1,1′-bis(diiso-propylphosphino)ferrocene (dippf), 1,1′-bis(dicyclohexylphosphino)ferrocene (dcpf), 1,1′-bis(ditert-butylphosphino)ferrocene (dtbpf), 1-diphenylphosphino-1′-ditert-butylphosphinoferrocene (dppdtbpf) or 1,1ʹ-bis(5-methyl-2-furanylphosphino)ferrocene (dfurpf)) compounds were examined as catalysts for the intramolecular ring-closing hydroamination of 3-(vinyloxy)propan-1-amine and the intermolecular hydroamination of phenylacetylene with a variety of phenylamine reagents. The catalytic activity of the corresponding [Au2(μ-Cl)(μ-PP)][BArF24] compounds that were generated in situ was also explored. Two new [Au2Cl2(μ-PP)] compounds with chiral bis(phosphino)ferrocene ligands (PP = 1,1′-bis(2R,5R-dimethylphospholanyl)ferrocene (R-dMeplf) or 1,1′-bis(2S,5S-dimethylphospholanyl)ferrocene (S-dMeplf)) were prepared, characterized spectroscopically and electrochemically, and evaluated as catalysts in the ring-closing hydroamination reaction. In addition, the X-ray structures of [Au2Cl2(μ-PP)] (PP = dppdtbpf, R-dMeplf and S-dMeplf) were determined.

Synthetic and mechanistic studies in enantioselective allylic substitutions catalysed by palladium complexes of a modular class of axially chiral quinazoline-containing ligands

The application of palladium complexes of a modular series of axially chiral phosphinamine ligands, the Quinazolinaps, to the enantioselective alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate and methyl dimethyl malonate is described. Complete conversions and enantiomeric excesses of up to 91% were obtained. To elucidate the solution structure of these complexes and their dynamic behaviour, 2D COSY and NOESY NMR experiments were carried out. An X-ray crystal structure of a palladacycle derived from 2-phenylQuinazolinap which possesses two Pd3Cl5 units is shown. Computational studies were also undertaken to allow qualitative predictions of diastereomeric ratios. The observed enantioselectivity was then rationalised in terms of combined spectroscopic and theoretical data. The catalytic results obtained are best interpreted by the reaction proceeding with nucleophilic attack on the allyl trans to the phosphorus donor atom of the major diastereomeric intermediate.

Leibniz‐Institute for Catalysis (LIKAT): From Basic Research to Practical Applications

Leibniz‐Institute for Catalysis (LIKAT): From Basic Research to Practical Applications

Binuclear Copper(I) Compounds with N‐Heterocyclic Thiolate and Diphosphane Ligands: Effects of Thiolate Ligands on Solid‐State Molecular Structures and Luminescence Properties

A series of four photoluminescent binuclear copper(I) compounds bearing phosphorus and sulfur donor atom ligands have been synthesized from reactions of copper(I) halides with the diphosphane dppe [1,2‐bis(diphenylphoshino)ethane] and the anions of three different N‐heterocyclic thiols, namely 5‐methyl‐1,3,4‐thiadiazole‐2‐thiol, 1‐phenyl‐1H‐tetrazole‐5‐thiol and ethyl 2‐thiouracil‐5‐carboxylate. Depending on the nature of the N‐heterocyclic thiol, the resulting compounds adopt two different structural motifs, having either a dppe‐bridged core, that is, [Cu2(κ‐S‐thiolate)2(dppe)2(µ‐dppe)], or a bis(thiolate)‐bridged core, that is, [Cu2(µ‐S‐thiolate)2(dppe)2], with a Cu2(µ‐S)2 cluster‐type core. The stabilization of the latter type of structure is rationalized by the presence of intramolecular hydrogen‐bonding interactions developed between two bridging N‐heterocyclic thiolate ligands positioned at the same side of the Cu2(µ‐S)2 core, which lead to short Cu···Cu interactions (ca. 2.6 Å), as it is evidenced by X‐ray crystallography studies and supported by Density‐Functional Theory (DFT) calculations. All compounds are photoluminescent and, upon UV‐light irradiation, they exhibit emission maxima ranging from about 470 to 510 nm, depending on the structural and geometric characteristics of the complexes. According to DFT calculations, the photoluminescence properties of the dppe‐bridged binuclear compounds originate from excited states having mainly a (M+L)LCT character, which result from [dCuI+π(thiolate)]→π*(phosphane) electronic transitions, while in the case of the thiolate‐bridged, cluster‐like binuclear compound the emitting excited states are also influenced by the short Cu···Cu interactions and appear to have also CC contributions in addition to an MLCT character. Furthermore, in the case of the dppe‐bridged binuclear complexes, the influence of the electronic nature of the thiolate group on the observed emission wavelength is demonstrated.

A Probabilistic Finite State Logic Machine Realized Experimentally on a Single Dopant Atom.

Exploiting the potential of nanoscale devices for logic processing requires the implementation of computing functionalities departing from the conventional switching paradigm. We report on the design and the experimental realization of a probabilistic finite state machine in a single phosphorus donor atom placed in a silicon matrix electrically addressed and probed by scanning tunneling spectroscopy (STS). The single atom logic unit simulates the flow of visitors in a maze whose topology is determined by the dynamics of the electronic transport through the states of the dopant. By considering the simplest case of a unique charge state for which three electronic states can be resolved, we demonstrate an efficient solution of the following problem: in a maze of four connected rooms, what is the optimal combination of door opening rates in order to maximize the time that visitors spend in one specific chamber? The implementation takes advantage of the stochastic nature of electron tunneling, while the output remains the macroscopic current whose reading can be realized with standard techniques and does not require single electron sensitivity.

Gas and Liquid Phase Diffusivities of Isomeric Metal Complexes Derived from Multifold Ring-Closing Metatheses: Ion Mobility Mass Spectrometry Trumps DOSY NMR

Isomeric octahedral osmium and rhenium complexes of formulas M(CO)y(X)z(P((CH2)n)3P) and M(CO)y(X)z(P(CH2)n−1CH2)((CH2)n)(P(CH2)n−1CH2) (n/M/y/z/X = 14/Os/2/2/Cl, 14/Os/2/2/Br, 14/Re/3/1/Cl, 18/Os/2/2/Br), in which the phosphorus donor atoms occupy trans positions, are examined by the title techniques. The former gyroscope-like complexes are spherical or ovoid in shape, whereas the latter have phosphacycle “flaps” that increase the volume. Both types diffuse at identical rates in C6D6 as assayed by DOSY NMR, but ions derived from the latter exhibit up to 10% slower drift times in the gas phase by ion mobility mass spectrometry (IMMS). Thus, IMMS, which is seldom applied to isomeric organometallic or coordination compounds, provides superior differentiation.

Hydrolysis of Me3SiCH2 groups on a double-chelating bis(ferrocenediyl)diphosphine coordinating to a Pt(0) center

The double-chelating diphosphine ligand PCH2SiMe3-bridged [1.1]ferrocenophane (1), in which two phosphorus donor atoms are doubly linked with two ferrocene groups and with a Me3SiCH2 group on each phosphorus center, was reacted with [Pt(PPh3)3] to form the tricoordinated Pt(0) complex [Pt(1)(PPh3)]. Refluxing of this complex with another equivalent of 1 in THF inadvertently containing traces of water was found to successively hydrolyze the four Me3SiCH2 groups of [Pt(1)2] to eventually form [Pt(2)2], in which all the initial Me3Si groups of [Pt(1)2] were replaced with hydrogens. The molecular structure of [Pt(2)2], as determined by X-ray analysis, shows stereochemical congestion between the two ligands. Since hydrolysis in refluxing THF did not proceed at all for both the free ligand 1 and the Pt(II) complex [PtCl2(1)], the stereochemical congestion of the Pt(0) complexes having two double-chelating diphosphine ligands is probably responsible for the observed hydrolysis.

Electrical current through individual pairs of phosphorus donor atoms and silicon dangling bonds.

Nuclear spins of phosphorus [P] donor atoms in crystalline silicon are among the most coherent qubits found in nature. For their utilization in scalable quantum computers, distinct donor electron wavefunctions must be controlled and probed through electrical coupling by application of either highly localized electric fields or spin-selective currents. Due to the strong modulation of the P-donor wavefunction by the silicon lattice, such electrical coupling requires atomic spatial accuracy. Here, the spatially controlled application of electrical current through individual pairs of phosphorus donor electron states in crystalline silicon and silicon dangling bond states at the crystalline silicon (100) surface is demonstrated using a high‐resolution scanning probe microscope operated under ultra‐high vacuum and at a temperature of 4.3K. The observed pairs of electron states display qualitatively reproducible current-voltage characteristics with a monotonous increase and intermediate current plateaus.

Multivalley envelope function equations and effective potentials for phosphorus impurity in silicon

We propose a system of real-space envelope function equations without fitting parameters for modeling the electronic spectrum and wave functions of a phosphorus donor atom embedded in silicon. The approach relies on the Burt-Foreman envelope function representation and leads to coupled effective-mass Schroedinger equations containing smooth effective potentials. These potentials result from the spatial filtering imposed on the exact potential energy matrix elements in the envelope function representation. The corresponding filter function is determined from the definition of the envelope function. The resulting effective potentials and the system of envelope functions jointly reproduce the valley-orbit coupling effect in the doped silicon. Including the valley-orbit coupling not only of the 1s, but also for 2s atomic orbitals, as well as static dielectric screening is found crucial to accurately reproduce experimental data. The measured binding energies are recovered with a maximum relative error of 1.53 %. The computed wave functions are in a good agreement with experimental measurements of the electron density provided by scanning tunneling microscopy.

Hydrogen Atom Desorption Induced By Electron Bombardment on Si Surface

1. Introduction Developments of nano-scale quantum device have been expected to open new approaches for information-processing. Among the various quantum devices proposed so far, a solid state qubit is one of the potential candidate devices to bring further progress to the modern computer technology. The nuclear spin qubit proposed by Kane, which is a phosphorus donor atom embedded in a Si lattice, has advantages such as longer relaxation time and higher process compatibility with Si LSI technology [1]. To manipulate a single dopant precisely on a Si substrate, a method employing electron bombardment from an STM tip on hydrogen-terminated Si surface has been proposed [2], [3]. Though successful experimental results including desorption of hydrogen atoms and adsorption of phosphorus atoms with atomic resolution have been reported, the relation between the number of desorbed hydrogen atoms and the number of bombarded electrons, which is one of fundamental issues for fabrication, has not been given in details. In this research, we study hydrogen atom desorption on Si(111) surface quantitatively for aiming at the development of atomic lithography. 2. Method First, a Si(111) wafer is chemically etched in aqueous NH4F solution (40%) in order to obtain hydrogen-terminated smooth surface for single atom desorption [4]. To exclude generation of etch pits, N2 bubbling has been employed prior to the etching to remove dissolved O2 in the solution. Next, the wafer is put into a vacuum chamber, and electrons are injected from an STM tip to the surface during STM image scanning. Tunneling electrons with appropriate energy can break Si-H bonds resulting in desorption of hydrogen atoms. 3. Experimental Results 3.1 Flattening of Si Surface Because the horizontal etching rate of Si(111) is larger than that of vertical one in the aqueous NH4F solution, flatter surface has been obtained. Our results show that the optimum etching time is about 15 minutes. Moreover, FT-IR result indicates that the surface is terminated by hydrogen atoms successfully. 3.2 Hydrogen Desorption Fig. 1 shows STM scan images of Si(111) before and after of hydrogen desorption. For this case, hydrogen desorption was done by STM scanning with +3.5 [V] and 4 [nA] sample bias, and all the hydrogen atoms in the scanned area were desorbed. On the other hand, surface images were obtained by STM scanning with -2. 5 [V] and 0.5 [nA] sample bias. Brighter region in the surface image (Fig. 1 (b)) corresponds to the hydrogen desorption area because dangling bonds increase electrical conductivity. Fig. 2 shows the ratio of hydrogen desorption area to the scanning area as functions of the tunneling current and the bias voltage. It can be seen that bias voltage lager than 3.1 [V] is required for desorption and desorption area increases approximately in proportion to the tunneling current. We also carried out electron bombardment without scanning. By applying a voltage pulse to the tip at the center position of an STM image and controlling the applied voltage, tunneling current, and pulse duration time, we can obtained suitable experimental parameters for minimizing the area of hydrogen desorption. The results show that a voltage pulse with 3.6 [V] amplitude and 70 [ms] duration desorbs hydrogens on about 30 sites. 4. Conclusion We have studied about the desorption of hydrogen atoms on Si(111) surface caused by electron bombardment, and confirmed by utilizing STM scanning that the desorption area is proportional to the tunneling current. Also, we demonstrated that the number of desorption sites can be minimized by applying a voltage pulse and controlling its duration time precisely. By extending the results obtained in this research, it could be possible to develop atomic lithography technique using STM.

Design and Characterization of Phosphine Iron Hydrides: Toward Hydrogen-Producing Catalysts.

Diamagnetic iron chloro compounds [(P(Ph)2N(Ph)2)FeCp*Cl] [1Cl] and [(P(Cy)2N(Ph)2)FeCp*Cl] [2Cl] and the corresponding hydrido complexes [(P(Ph)2N(Ph)2)FeCp*H] [1H] and [(P(Cy)2N(Ph)2)FeCp*H] [2H] have been synthesized and characterized by NMR spectroscopy, electrochemical studies, electronic absorption, and (57)Fe Mössbauer spectroscopy (P(Ph)2N(Ph)2 = 1,3,5,7-tetraphenyl-1,5-diphospha-3,7-diazacyclooctane, P(Cy)2N(Ph)2 = 1,5-dicyclohexyl-3,7-diphenyl-1,5-diphospha-3,7-diazacyclooctane, Cp* = pentamethylcyclopentadienyl). Molecular structures of [2Cl], [1H], and [2H], derived from single-crystal X-ray diffraction, revealed that these compounds have a typical piano-stool geometry. The results show that the electronic properties of the hydrido complexes are strongly influenced by the substituents at the phosphorus donor atoms of the P(R)2N(Ph)2 ligand, whereas those of the chloro complexes are less affected. These results illustrate that the hydride is a strong-field ligand, as compared to chloride, and thus leads to a significant degree of covalent character of the iron hydride bonds. This is important in the context of possible catalytic intermediates of iron hydrido species, as proposed for the catalytic cycle of [FeFe] hydrogenases and other synthetic catalysts. Both hydrido compounds [1H] and [2H] show enhanced catalytic currents in cyclic voltammetry upon addition of the strong acid trifluoromethanesulfonimide [NHTf2] (pKa(MeCN) = 1.0). In contrast to the related complex [(P(tBu)N(Bn))2FeCp(C6F5)H], which was reported by Liu et al. (Nat. Chem. 2013, 5, 228-233) to be an electrocatalyst for hydrogen splitting, the here presented hydride complexes [1H] and [2H] show the tendency for electrocatalytic hydrogen production. Hence, the catalytic direction of this class of monoiron compounds can be reversed by specific ligand modifications.

Synthesis of bicyclic diphosphine having a P−P bond doubly clamped with two 1,8-naphthalenediyl groups

A synthetic route was developed for a novel bicyclic diphosphine 5 in which two structurally robust 1,8-naphthalenediyl groups clamp the P–P bond of the diphosphine to form a butterfly structure. The bicyclic framework was synthesized by a ring-opening dimerization of a strained four-membered phosphacycle of iPr2NP-peri-bridged naphthalene 8. A toluene solution of 8 was heated for 2days in the presence of O2 and one equivalent of H2O to give a mixture of oxides of the target diphosphine 5, then the mixture of oxides was reduced with HSiCl3 to afford 5 in a moderate yield. The crystal structure of 5 confirmed that the P–P bond and the two naphthalene groups form a butterfly molecular structure, and the two lone pairs on the respective phosphorus centers are disposed in a synperiplanar configuration. These two phosphorus donor atoms bind two AuCl fragments to form a unique “U-shape” binuclear complex (μ-5)-[AuCl]2 in which the two Au(I) centers are separated by ca. 4.4Å that indicates the negligible intramolecular Au–Au interaction. In the crystal, the two binuclear complexes interlocked with each other through multiple intermolecular Au–Au interactions between the two U-shape units.

Probing substituent effects in phosphinoamine ligands using Mo(CO)5L complexes

Recent work has revealed substantial differences in the structure, spectroscopic properties, and reactivity of heterobimetallic Zr/Co complexes of the general form XZr(R′NPR2)3CoY (R′=iPr, 2,4,6-trimethylphenyl, 3,5-dimethylphenyl; R=Ph, iPr; X, Y=halides or neutral donor ligands) as a function of nitrogen and phosphorus donor atom substituents. To probe the electronic differences between these ligands, a series of Mo(CO)5(R2PNHR′) complexes has been synthesized (R=Ph, R′=iPr (2a); R=iPr, R′=iPr (2b), 2,4,6-trimethylphenyl (2c), 3,5-dimethylphenyl (2d), 4-methylphenyl (2e), 4-trifluoromethylphenyl (2f), 4-methoxyphenyl (2g)). Thermolysis of Mo(CO)6 with the corresponding phosphinoamine ligands 1a–1g affords 2a–2g. The infrared carbonyl stretching frequencies of these complexes have been compared to probe the effects of phosphorus and nitrogen substituents on the electronic properties of the phosphinoamine ligands.

Dual Homogeneous and Heterogeneous Pathways in Photo- and Electrocatalytic Hydrogen Evolution with Nickel(II) Catalysts Bearing Tetradentate Macrocyclic Ligands

A series of nickel(II) complexes bearing tetradentate macrocyclic N4, N3S, and N3P ligands were synthesized, and their photocatalytic activity toward proton reduction has been investigated by using [Ir(dF(CF3)ppy)2(dmbpy)]PF6 (dF(CF3)ppy = 2-(2,4-difluorophenyl)-5-trifluoromethylpyridine and dmbpy = 4,4′-dimethyl-2,2′-dipyridyl) as the photosensitizer and triethylamine (TEA) as the sacrificial reductant. The complex [Ni(L4)]2+ (L4 = 2,12-dimethyl-7-phenyl-3,11,17-triaza-7-phospha-bicyclo[11,3,1]heptadeca-1(17),13,15-triene), which bears a phosphorus donor atom, shows the highest efficiency with TON up to 5000 under optimized conditions, while the tetraaza macrocyclic nickel complexes [Ni(L1)]2+ and [Ni(L2)]2+ (L1 = 2,12-dimethyl-3,7,11,17-tetra-azabicyclo[11.3.l]heptadeca-1(17),2,11,13,15-pentaene; L2 = 2,12-dimethyl-3,7,11,17-tetra-azabicyclo[11.3.l]heptadeca-1(17),13,15-triene) show lower photocatalytic activities. Transient UV–vis absorption and spectroelectrochemical experiments show that Ni(II) is re...

Stereoelectronic and Catalytic Properties of Chiral Cyclometalated Phospha-palladium and -platinum Complexes

The stereoelectronic properties of palladium(II) and platinum(II) complexes containing ortho-metalated (1-(diphenylphosphino)ethyl)naphthalene were examined by X-ray crystallography in the solid state and by NMR spectroscopy in solution. The studies revealed that the aromatic carbon induced a significantly stronger electronic trans-influence than the phosphorus donor within the same five-membered chelate. Both the organopalladium and organoplatinum chelate complexes were formed with classical hard oxygen and soft phosphorus donor atoms. Computational studies further confirmed the observations in the solid state and solution that the C–metal bond in the trans C–Pt–O moiety has a stronger π-character than that in the trans C–Pt–P moiety. Both organometallic units are efficient catalysts for the asymmetric P–H addition reaction. They showed almost identical efficiency in dichloromethane, but their reactivity in THF is markedly different.