Novel bicyclic hexanuclear copper(I) aggregate: Structure and solid state P CPMAS NMR spectra of [(Cu3L3)2] and [Cu(PPh3)2L] complexes of N-(diisopropoxythiophosphinyl)-N′-phenylthiourea (HL)

A new complex of N-thiophosphorylthiourea PhNHC(S)NHP(S)(OiPr)₂ (HL) of formula [(Cu₃L₃)₂] has been synthesized and characterized by single crystal X-ray diffraction, FT-IR, ¹H, ³¹P NMR in solution and by ³¹P CPMAS NMR spectroscopy in the solid state. A comparison of the structure and the spectral parameters of [(Cu₃L₃)₂] with those of the mononuclear analogue [Cu(PPh₃)₂L] was performed. In the solid state the aggregate [(Cu₃L₃)₂] represents the first example of a spontaneous “side-by-side” association of two neutral cyclic [Cu₃L₃] moieties using two Cu-S-Cu bridges formed by the sulfur atoms of the PS-groups. The values of the ¹J(³¹P-^63,65Cu) and ²J(³¹P-³¹P) coupling constants of the [Cu(PPh₃)₂]⁺ moiety in the solid state spectra are reported.     

Long-Range 31P-31P Spin Coupling Constants in the 31P NMR Spectra of Phosphite Triesters

Abstract

Data are presented on the magnitudes of ⁵ J _pp and ⁶ J _PP spin-spin coupling constants in the ³¹P NMR spectra of a variety of novel polyphosphite triesters.     

"Through-space" nuclear spin-spin J(PP) coupling in tetraphosphine ferrocenyl derivatives: a (31)P NMR and X-ray structure correlation study for coordination complexes

Herein, we report on (31)P(31)P solution-phase "through-space" nuclear spin-spin coupling constants (J(PP)) from a novel family of organometallic tetraphosphine nickel and palladium complexes. These J(PP) constants were accurately determined through NMR iterative simulation based on the second-order spectra obtained for the compounds. The corresponding solid-state X-ray structures of the complexes were determined, and the "through-space" P.P distances are reported. Due to the blocked conformation of the species in solution, a qualitative and semiquantitative experimental correlation is obtained, which links the geometric parameters and the intensity of the corresponding P.P coupling constant. The lone-pair overlap theory developed for (19)F(19)F and (15)N(19)F "through-space" couplings in organic compounds [J. Am. Chem. Soc. 1973, 95, 7747-7752; 2000, 122, 4108-4116] appears to be a reliable foundation on which to account for our results. Based on the reported observations, the lone-pair overlap model is extended to "through-space" (31)P(31)P coupling, and the model is broadened to encompass metal orbital contributions for coordination complexes. Some of the predictions and consequences of the proposed theory are discussed.     

An Investigation of 1:1 Adducts of Gallium Trihalides with Triarylphosphines by Solid‐State 69/71Ga and 31P NMR Spectroscopy

Several 1:1 adducts of gallium trihalides with triarylphosphines, X₃Ga(PR₃) (X=Cl, Br, and I; PR₃=triarylphosphine ligand), were investigated by using solid‐state ^69/71Ga and ³¹P NMR spectroscopy at different magnetic‐field strengths. The ^69/71Ga nuclear quadrupolar coupling parameters, as well as the gallium and phosphorus magnetic shielding tensors, were determined. The magnitude of the ⁷¹Ga quadrupolar coupling constants (C_Q(⁷¹Ga)) range from approximately 0.9 to 11.0 MHz . The spans of the gallium magnetic shielding tensors for these complexes, δ₁₁?δ₃₃, range from approximately 30 to 380 ppm; those determined for phosphorus range from 10 to 40 ppm. For any given phosphine ligand, the gallium nuclei are most shielded for X=I and least shielded for X=Cl, a trend previously observed for In^III–phosphine complexes. This experimental trend, attributed to spin‐orbit effects of the halogen ligands, is reproduced by DFT calculations. The signs of C_Q(^69/71Ga) for some of the adducts were determined from the analysis of the ³¹P NMR spectra acquired with magic angle spinning (MAS). The ¹J(^69/71Ga,³¹P) and ΔJ(^69/71Ga, ³¹P) values, as well as their signs, were also determined; values of ¹J(⁷¹Ga,³¹P) range from approximately 380 to 1590 Hz. Values of ¹J(^69/71Ga,³¹P) and ΔJ(^69/71Ga,³¹P) calculated by using DFT have comparable magnitudes and generally reproduce experimental trends. Both the Fermi‐contact and spin‐dipolar Fermi‐contact mechanisms make important contributions to the ¹J(^69/71Ga,³¹P) tensors. The ³¹P NMR spectra of several adducts in solution, obtained as a function of temperature, are contrasted with those obtained in the solid state. Finally, to complement the analysis of NMR spectra for these adducts, single‐crystal X‐ray diffraction data for Br₃Ga[P(p‐Anis)₃] and I₃Ga[P(p‐Anis)₃] were obtained.     

Intermolecular spin–spin coupling constants between P atoms

This paper reports the study by NMR spectroscopy and ab initio methods of the structure of 3,4-dimethyl-1-cyanophosphole and its dimer. The dimer presents a P···P interaction of the pnictogen type due to the presence of σ-holes. NMR of the monomer was recorded in CDCl₃ solution while NMR of the dimer corresponds to the solid state (CPMAS) experiments. The ^2pJ_PP spin–spin coupling constant has not been measured, but calculated at the B3LYP level. AIM, NBO and ELF methodologies have been used to describe the electronic structure of the dimer.     

NMR-spektroskopische Untersuchungen an 15N-markierten N-Methyl-imidodiphosphorsäure-Derivaten

NMR Spectroscopic Studies of ¹⁵N Labelled N-Methyl-imidodiphosphoric Acid Derivatives ¹⁵N labelled compounds (EtO)_mCl_2?m(O)P? NMe? P(O)(OEt)_nCl_2?n (m = 0–2, n = 0–2) were prepared as a mixture and investigated by means of ³¹P and ¹⁵N NMR spectroscopy. The chemical shift values δ_P and δ_N, and the coupling constants ¹J_PN and ²J_PP are discussed and interpreted qualitatively by semiempirical quantumchemical calculations (CNDO/2) using POPLE 'S ΔE-model.     

Coordination chemistry of tetra- and tridentate ferrocenyl polyphosphines: an unprecedented [1,1'-heteroannular and 2,3-homoannular]-phosphorus-bonding framework in a metallocene dinuclear coordination complex

PalladiumII and nickelII halide complexes of the ferrocenyl polyphosphines 1,1',2,3-tetrakis(diphenylphosphino)ferrocene (1), and 1,1',2-tris(diphenylphosphino)-4-tert-butylferrocene (5) were prepared and characterized by multinuclear NMR. The metallo-ligand 1, the palladium [Pd2Cl4(1)] (3b) and nickel [NiCl2(5)] (6) coordination complexes were additionally characterized by X-ray diffraction crystallography. The behavior of 1 toward coordination to nickel and palladium was surprisingly different because the coordination of a second metal center after the initial 1,2-phosphorus-bonding of nickel was markedly difficult. The preference of nickel for 1,2-P coordination on 1,1'-bonding was confirmed by the exclusive formation of 6 from 5. The changes noted between the solid state structure of the ligand 1 and the structure obtained for the dinuclear palladium complex 3b reveal the rotational flexibility of this tetraphosphine. This flexibility is at the origin of the unique framework for a metallocenic dinuclear metal complex in which both coexist a 1,1'-heteroannular chelating P-bonding and a 2,3-homoannular chelating P-bonding with two palladium centers. Some reported specimens of ferrocenyl polyphosphines of constrained geometry have previously revealed that phosphorus lone pair overlap can lead to very intense "through-space" 31P31P nuclear spin-spin coupling constants (JPP) ( J. Am. Chem. Soc. 2004, 126 (35), 11077-11087] in solution phase. In these cases, an internuclear distance between heteroannular phosphorus atoms below 4.9 A, with an adequate orientation of the lone-pairs in the solid state and in solution, was a necessary parameter. The flexibility of the new polyphosphines 1 and 5 does not allow that spatial proximity (internuclear distances between heteroannular phosphorus above 5.2 A in the solid state); accordingly the expected through-space nuclear spin-spin coupling constants were not detected in any of their coordination complexes nor in 1.     

Conformational analysis of 2-OAryl-2-oxo-4,6-dimethyl- and -4-methyl-1,3,2λ5-dioxaphosphorinanes. Spectroscopic,X-Ray,and solid-state 13C and 31P studies

Results of IR and ¹H, ¹³C, and ³¹P NMR studies of the anancomeric title compounds ( 2–5 ) and compound 1 (Scheme 1) are analyzed to search for the existence of high-energy boat or twist-boat conformations in the equatorial epimers. While the difference in frequencies (Δν)_P=O between the axial and equatorial compounds and ¹³C NMR J_POCC and anti J_POCCH3 values suggest the participation of twist-boat conformations for the equatorial isomers, coupling constants in ¹H NMR J_H4H5a or J_H6H5a and J_H4H5e or J_H6H5e of the equatorial isomers 2e–4e along with the lack of a large ³J_PH in ³¹P NMR are consistent with predominant chair conformations. In addition, an X-ray structure of the equatorial 2-p-nitrophenoxy-2-oxo-cis-4,6-dimethyl-1,3,2-dioxaphosphorinane ( 4e ) showed that the molecule adopts a chair conformation with no severe ring flattening in the OPO region in the solid state. X-ray structures of trans- 4 and trans- 5 displayed chair conformations with mild ring flattening especially in the axial methyl region, presumably as a result of the steric methyl-oxygen interaction. CPMAS ¹³C and ³¹P NMR spectra of 4a and 4e provide evidence against the presence of a significant contribution of a twist-boat conformation in solid equatorial 4e . The NMR spectral analysis of 1e , on the other hand, suggests a substantial contribution of a twist conformation as well as, possibly, some contribution of the inverted chair. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8: 509–516, 1997     

Solid‐State NMR Characterization of Wilkinson’s Catalyst Immobilized in Mesoporous SBA‐3 Silica

The Wilkinson’s catalyst [RhCl(PPh₃)₃] has been immobilized inside the pores of amine functionalized mesoporous silica material SBA‐3 and The structure of the modified silica surface and the immobilized rhodium complex was determined by a combination of different solid‐state NMR methods. The successful modification of the silica surface was confirmed by ²⁹Si CP‐MAS NMR experiments. The presence of the T_n peaks confirms the successful functionalization of the support and shows the way of binding the organic groups to the surface of the mesopores. ³¹P‐³¹P J‐resolved 2D MAS NMR experiments were conducted in order to characterize the binding of the immobilized catalyst to the amine groups of the linkers attached to the silica surface. The pure catalyst exhibits a considerable ³¹P‐³¹P J‐coupling, well resolvable in 2D MAS NMR experiments. This J‐coupling was utilized to determine the binding mode of the catalyst to the linkers on the silica surface and the number of triphenylphosphine ligands that are replaced by coordination bonds to the amine groups. From the absence of any resolvable ³¹P‐³¹P J‐coupling in off‐magic‐angle‐spinning experiments, as well as slow‐spinning MAS experiments, it is concluded, that two triphenylphosphine ligands are replaced and that the catalyst is bonded to the silica surface through two linker molecules.     

Beiträge zur Chemie des Phosphors. 64 [1]. Zur quasicyclischen Konformation der Organylphosphide M2(PR)n′ [MK,Na]

Contributions to the Chemistry of Phosphorus. 64. About the Quasicyclic Conformation of the Organylphosphides M₂(PR)_n′[M = K, Na] The organyl tetraphosphides M₂(PR)₄ (M = K, Na) and – as can be assumed with a high probability – the corresponding triphosphides M₂(PR)₃ exhibit a quasicyclic conformation with a twofold intramolecular metal bridge between the terminal P atoms. This structure becomes evident from the following ³¹P n.m.r. spectroscopic observations for the tetraphosphides: For the salts M₂(PR)₄ (M = K, Na) only a single configuration isomer is observed indicating that a configuration selecting “cyclization reaction” takes place. Beyond it, the ²J_PP coupling constants have the same range of magnitude as in five-membered heterocyclophosphanes. Moreover, the ³J_PP couplings between the “terminal” P atoms possess unusual high values. The alternative monocyclic structure with a single metal bridge is not compatible with a configuration rule for five-membered phosphanes which describes the relation of magnitudes of cis- and trans-²J_PP couplings.     

1H-, 13C-UND 31P-NMR-SPEKTROSKOPISCHE UNTERSUCHUNGEN AN BIS-(DIALKOXYTHIOPHOSPHORYL)-UND-(DIALKOXYPHOSPHORYL)-SULFANEN UND-POLYSULFANEN

Abstract

Compounds of the following structure

(R¹O)₂(X)P[sbnd]Y–P(X)(OR²)₂

(X = O, Y = S_n (n = 1–4), R¹ = R² = Me, iPr;

X = S, Y = S_n (n = 1–4), R¹, R² = Me, Et, iPr, iBu;

X = S, Y = S-Se-S, S-Te-S, R¹ = R² = Me

were prepared and their NMR spectra were analysed. Depending on the number of sulfur atoms, bonded between the phosphorus atoms, typical ranges of the P-P coupling constants were found for the different sulfanes investigated: ²J_PP from-10 to-20 Hz, ³J_PP less than 3 Hz, ⁴J_PP from +10 to +13 Hz and ⁵J_PP less than 1 Hz. For the small vicinal coupling constants and the relatively large values of ⁴J_PP different possibilities of their interpretation are given.     

Diselenadiphosphetandiselenide und Triselenadiphospholandiselenide – Synthese und Charakterisierung mittels 31P‐ und 77Se‐Festkörper‐NMRSpektroskopie

Diselenadiphosphetane Diselenides and Triselenadiphospholane Diselenides – Synthesis and Characterization by ³¹P and ⁷⁷Se Solid‐State NMR Spectroscopy 1,3‐Diselena‐2,4‐diphosphetane‐2,4‐diselenides (RPSe₂)₂ with R = Me, Et, t‐Bu, Ph, 4‐Me₂NC₆H₄, 4‐MeOC₆H₄ have been synthesized by different methods. The insoluble compounds were investigated by ³¹P and ⁷⁷Se solid‐state NMR and the purity of the compounds has been checked by their CP MAS sideband NMR spectra. The structure of the investigated compounds has been confirmed by the isotropic and anisotropic values of the chemical shifts and the ¹J_P–Se coupling constants. In addition, two new 1,2,4‐triselena‐3,5‐diphospholane‐3,5‐diselenides, (RPSe₂)₂Se (R = Me, Et), formed under similar synthesis conditions, were investigated. Their structure was derived from the ⁷⁷Se satellites of ³¹P solution spectra and from solid‐state spectra. For (t‐BuPSe₂)₂ the experimentally obtained principal values of phosphorus and selenium shielding tensors are compared with values from IGLO calculations (HF und SOS DFPT). The calculated orientations of the principal axes are discussed.     

Synthese et proprietes chimiques de deux diazoalcanes α-thiophosphores. observation d'un couplage 4jpp

Transfer of diazo and/or azide groups to the methylene of phosphine sulfides 1 Ph₂P(S) CH₂R, leads to the diazoalkanes Ph₂P(S)CN₂R 2b and 2c and azides Ph₂P(S)CHN₃R 3a and 3c in good yields. Thermolysis and photolysis in various media are studied. The 1,3-dipolar addition of 2c on trans dibenzoyléthylène and ethylfumarate is followed by Ph₂P(S) group migration. The corresponding carbenes give very complex reactions causing P-C bond breaking. New coupling constants ⁴J_PP and J_PC are observed.     

The first naphthodiazaphosphorinane in the solid phase; syntheses, spectroscopic studies and X-ray crystallography of some new 1,3,2-diheterophosphorus compounds

New heterocyclic compounds of diazaphosphorinanes, diazaphospholes, and oxazaphospholes were synthesized and characterized by ¹H, ¹³C, ³¹P, NMR, IR spectroscopy, and CHN elemental analysis. The 3D structure of compound (5) was determined by X-ray crystallography. Since benzo- or naphthodiazaphospholes/diazaphosphorinanes containing aromatic rings are usually unstable in the solution state, their single crystal structures are rarely reported and, to the best of our knowledge, this structure is the first occasion of naphthodiazaphosphorinanes obtained here. It is noticeable that the P=O and C=O bonds are closer to syn than anti configuration and the P=O bond is placed in a pseudo-equatorial position. This structure produced a 3D polymeric chain via strong hydrogen bonds and electrostatic short contacts. Due to the ring strain of five-membered rings, for all diazaphospholes great ² J(PNH_endocyclic) coupling constants (about 18.0 Hz), as well as high ^2,3 J(P,C) coupling constants for the aromatic carbon atoms connected to the five-membered ring (about 14.5, 13.5 Hz, respectively) were measured. Replacement of one NH group in a diazaphosphole ring by an oxygen atom caused exceedingly decreased ring strain and hence highly diminished ² J(PNH_endocyclic) coupling constant. Furthermore, ³¹P NMR spectra of oxazaphospholes, like the spectra of diazaphosphorinanes, indicated highly shielded phosphorus atoms relative to those of their diazaphospholes analogs. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Rhodium(III) Complexes Featuring Coordinated CF3 Appendages

The synthesis and characterisation of a homologous series of rhodium 2,2′-biphenyl complexes featuring intramolecular dative bonding of the nominally inert and weakly coordinating trifluoromethyl group are described. Presence of these interactions is evidenced in the solid state using X-ray diffraction, with Rh−F contacts of 2.36–2.45 Å, and in solution using NMR spectroscopy, through hindered C−CF₃ bond rotation and the presence of time-averaged ¹J_RhF and ²J_PF coupling.     

Assignment of the 13C NMR resonances in trialkylphosphines from spin-lattice relaxation time measurements

Analysis of the ¹³C NMR chemical shift and coupling constant data for a number of straight-chain aliphatic trialkylphosphines and their transition metal carbonyl complexes suggests that complexation leads to: (1) a deshielding of C(1) and an increase in ¹J(¹³C³¹P), (2) a slight shielding of C(2) and a decrease in ²J(¹³C³¹P), and (3) little or no change in the chemical shift for C(3) and a slight increase in ³J(¹³C³¹P). Application of these rules to the assignment of the ¹³C NMR spectrum of P(butyl)₃ led to conflict with prior work. A study of segmental motion in these derivatives via spin-lattine (T₁) relaxation time measurements was therefore performed, and these data are in complete agreement with the proposed assignments. These generalizations must be applied with care, however, since the presence of either unsaturation or branching near the phosphorus can interfere with this pattern.     

NMR-spektroskopische Untersuchungen an Mercaptophosphazenen. II. NMR-spektroskopische Untersuchungen an 15N-markierten Mercaptophosphazenen

N.M.R. Spectroscopic Investigations of Thiophosphazenes. II. N.M.R. Spectroscopic Investigations of ¹⁵N Labelled Thiophosphazenes Completely ¹⁵N labelled compounds of the type ¹⁵N₃P₃Cl_6?n(SR)_n, R = Et or Ph; n = 0, 2, 4, or 6, and of the type ¹⁵N₄P₄Cl_8?n(SR)_n, R = Et; n = 0, 4, or 8, were prepared and investigated by means of both ³¹P n.m.r. spectroscopy and ¹⁵N n.m.r. spectroscopy respectively. The coupling constants ²J_PP, in some cases only found by simulating the spectra, and the coupling constants ¹J_PN are given. The values of these coupling constants and their relation are discussed. The general tendency is visible, that with increasing coupling constant ¹J_PN the coupling constant ²J_PP decreases. With increasing grade of substitution n the ¹⁵N chemical shifts are changed to higher fields.     

NMR Studies of the Phosphazene/Phosphazane Rearrangement

In compounds such as hydroxy, methoxy and ethoxycyclophosphazenes a phosphazene/ phosphazane rearrangement occurs. In this process the electronic structure of the PN ring system changes under reduction of the endocyclic double bonds. A decrease of the s bond order of the PN bondings results in a decrease of the scalar couplings ¹J_PN and ²J_PP. In addition, considering the solid‐state ³¹P NMR spectra, significant differences between the phosphazene and phosphazane forms can be observed caused by a change of the local symmetry at the phosphorus atom. In the case of cyclotriphosphazenes a local C_2v symmetry exists (strictly valid for these compounds only) and the shielding (shift) tensor is characterized by a small anisotropy as well as a small axiality. Contrary to this in phosphazanes the phosphoryl bond is dominating the chemical shift tensor, characterized by a double to triple anisotropy and a high axiality. Quantum chemical GAUSSIAN calculations reflect these differences between phosphazenes and phosphazanes.     

Conformational Studies of a Six-Membered Phostone

Abstract

Although 1,3,2-dioxaphosphorinanes generally assume chair conformations,¹ there are examples in which the ring adopts the boat or twist-boat form.¹ Recent studies on the synthesis, stereochemistry, and reactivity of 2-alkoxy-2-oxo-1,2-oxaphosphorinanes (phostones) have revealed both cis and trans isomers of 3-(diphenylhydroxymethyl)-2-ethoxy-2-oxo-1,2-axaphosphorinane² to assume a chair conformation in the solid state. In the present work, the conformational properties of cis and trans-3-methoxycarbonyl-2-methoxy-2-oxo-1,2-oxaphosphorinanes were investigated by X-ray analysis, variable temperature ³¹P, ¹H and ¹H{³¹P} NMR spectroscopy, molecular mechanics, and semiempirical calculations. The X-ray crystal structure of the trans isomer revealed a chair dormation with equatorial phosphoryl and carbomethoxy groups. No changes were observed in the ³¹P NMR spectra of either isomer in the temperature range of 183–333 K. A complete set of vicinal J_HH coupling constants was extracted from the ¹H{³¹P} spectra of each isomer taken at five temperatures over the range of 213–293 K and refined by simulation of the spectra. The best-fit analysis of this data using a generalized Karplus equation³ revealed that the conformation of the trans isomer in solution was close to that found in the solid state. This conformation corresponded to the global energy minimum calculated by both molecular mechanics and PM3 semiempirical method. A substantial contribution from an inverted chair conformation of the cis isomer had to be assumed to achieve a reasonable fit of the coupling constants calculated from the generalized Karplus equation.     

Sur la Similitude des Déformations du Noyau Cyclohexanonique Induites par les Groupes Tertiobutyle et gem-Diméthyle

X-ray and NMR (250 MHz) data for chlorinated 4,4-dimethylcyclohexanones lead to the following conclusions: carbonyl and chlorine substituent effects on ²J and ³J coupling constants are similar to those observed for 4-tert-butylcyclohexanones. In other respects, the gem dimethyl and the tert-butyl groups induce on the ring similar large ⁴J coupling constants (H-3′? C-3? C-4? C-5? H-5′); the results can be interpreted in terms of local gemoetric deformations and additivity of these deformations. The determination of dihedral angles by Lambert's method and from X-ray data shows the identity of the structures in the solid state and the dissolved state and confirms the great structural similarity between 4-tert-butyl- and 4,4-dimethylcyclohexanone derivatives.