Phosphorus-31 Nuclear Magnetic Resonance Spectra of Co-ordination Compounds

Nixon, John F.; Pidcock, Alan

doi:10.1016/s0066-4103(08)60325-7

Cited by 154 publications

(64 citation statements)

References 72 publications

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“…As would be expected, the PtP A coupling constant in 9 is larger than in 8, reflecting the increase of s character on the Pt-P bond, caused by the presence of the more electronegative fluorine, bonded through the P A , in the first complex 10 . The 31 P{ 1 H} NMR studies also suggest an increase in the magnitude of 1 J(PtP A ) on changing the group bonded to the oxygen atom in the phosphorus from -CH 2 CH 2 CH 2 -to 1,2-benzo.…”

Section: Syntheses and Characterisation Of Platinum(0) Complexesmentioning

confidence: 53%

“…A long range 3 J(P B F) coupling constant is also observed in the 31 P{ 1 H} NMR spectrum of 9. The 31 P{ 1 H} NMR studies of complexes 10 -14 showed that they posses a cis arrangement around the platinum centre since the values for the 2 J(P A P B ) coupling constants lie between 23 and 41 Hz and those for the 1 J(PtP) are typical for this kind of complexes 10 .…”

Section: Syntheses and Characterisation Of Platinum(0) Complexesmentioning

confidence: 96%

“…Table 3), with the exception to the fluoro derivative, which might be due to the small size of fluorine, compared to chlorine. (Table 3), whereas ligand 4 affords complex 17 with cis configuration around the metallic centre 10 . Again, an explanation in terms of the combined sizes of palladium atom and the halogen bonded through the phosphorus can be given.…”

Section: Syntheses and Characterisation Of Platinum(ii) Complexesmentioning

confidence: 99%

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Syntheses and 31P NMR studies of transition metal complexes containing derivatives of dioxaphospholane and dioxaphosphorinane

Matos¹,

Costa²,

Knupp³

et al. 2000

J. Braz. Chem. Soc.

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A síntese de vários complexos de Pt(II), Pt(0) e Pd(II) com 2-cloro-1,3,2-dioxafosfolana, 2-fluoro-1,3,2-dioxafosfolana, 2-cloro-4,5-benzo-1,3,2-dioxafosfolana, 2-fluoro-4,5-benzo-1,3,2-dioxafosfolana, 2-cloro-1,3,2-dioxafosforinana e 2-fluoro-1,3,2-dioxafosforinana é descrita. Estudos de RMN de 31 P{ 1 H} destes complexos revelam alguns aspectos inexplorados em relação às constantes de acoplamento 1 J(PtP), os quais chamam a atenção para o conceito de ácidos e bases duros e macios. Este trabalho mostra também as diferenças espectroscópicas de RMN de 31 P{ 1 H} entre isômeros cis e trans.The syntheses of various complexes of Pt(II), Pt(0) and Pd(II) with 2-chloro-1,3,2-dioxaphospholane, 2-fluoro-1,3,2-dioxaphospholane, 2-chloro-4,5-benzo-1,3,2-dioxaphospholane, 2-fluoro-4,5-benzo-1,3,2-dioxaphospholane, 2-chloro-1,3,2-dioxaphosphorinane, 2-fluoro-1,3,2-dioxaphosphorinane are reported. 31 P{ 1 H} NMR studies of these complexes reveals some aspects still unexplored in terms of the magnitude of the coupling constants 1 J(PtP), which brings light to the soft and hard acid-base concept. This work also shows the 31 P{ 1 H} nmr spectroscopic differences between cis and trans isomers.

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Section: Syntheses and Characterisation Of Platinum(0) Complexesmentioning

confidence: 53%

Section: Syntheses and Characterisation Of Platinum(0) Complexesmentioning

confidence: 96%

Section: Syntheses and Characterisation Of Platinum(ii) Complexesmentioning

confidence: 99%

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Syntheses and 31P NMR studies of transition metal complexes containing derivatives of dioxaphospholane and dioxaphosphorinane

Matos¹,

Costa²,

Knupp³

et al. 2000

J. Braz. Chem. Soc.

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“…The unidentate coordination mode of dppm in 2 is inferred from the presence of two mutually coupled nonequivalent phosphorous 31 P{ 1 H} NMR ressonances. The high field signal has a chemical shift very similar to that of the free molecule 18 . The downfield ressonances due to the coordinated phosphorous demonstrated a decrease in coordination shift, defined as δ complex -δ free ligand 18 .…”

Section: Ir and 31 P{ 1 H} Nmr Datamentioning

confidence: 90%

“…The high field signal has a chemical shift very similar to that of the free molecule 18 . The downfield ressonances due to the coordinated phosphorous demonstrated a decrease in coordination shift, defined as δ complex -δ free ligand 18 . The 31 P{ 1 H} NMR spectrum of 3 is similar to that of 2; however two singlets were observed indicating that the two phosphorous atoms are not coupled due to the greater distance between them in dppf than in dppm 19 .…”

Section: Ir and 31 P{ 1 H} Nmr Datamentioning

confidence: 90%

Electrochemical and spectroscopic studies of tungstencarbonyl complexes containing nitrogen and phosphorous ligands

Haddad¹,

Miranda²,

Ananias³

et al. 2000

J. Braz. Chem. Soc.

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Este trabalho tratou da síntese, caracterização espectroscópica e do comportamento eletroquímico dos compostos [W(CO) 4 (bipy)] (1), [W(CO) 3 (bipy)(dppm)] (2) e [W(CO) 3 (bipy)(dppf)] (3), bipy = 2,2'-bipiridina; dppm = bis(difenilfosfina)metano; dppf = 1,1'-bis(difenilfosfina)ferroceno. Os dados provenientes das espectroscopias no infravermelho e de RMN 31 P{ 1 H} mostraram que o tungstênio apresenta uma geometria de coordenação octaédrica com as fosfinas atuando como ligantes monodentados. Os estudos eletroquímicos foram realizados empregando-se as técnicas de voltametria cíclica e coulometria a potencial controlado. Os voltamogramas cíclicos mostraram que os carbonil complexos contendo ligantes fosforados apresentam uma maior estabilidade frente à oxidação do que o composto (1).The present work deals with the synthesis, spectroscopic investigation and electrochemical behaviour of the compounds [W(CO) 4 (bipy)] (1), [W(CO) 3 (bipy)(dppm)] (2) and [W(CO) 3 (bipy)(dppf)] (3), bipy = 2,2'-bipyridine; dppm = bis(diphenylphosphino)methane; dppf = 1,1'-bis(diphenylphosphino)ferrocene. The IR and 31 P{ 1 H} NMR spectroscopic data have shown an octahedral coordination geometry for the tungsten atom with the diphosphines acting as monodentate ligands. The electrochemical behaviour of the complexes was investigated by cyclic voltammetry and controlled potential coulometry. Cyclic voltammograms have indicated that the compounds containing diphosphines ligands are more stable towards oxidation than compound (1).

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Structural and Theoretical Studies ofortho-Substituted Triphenylphosphane Ligands and Their Rhodium(I) Complexes

Suomalainen

Jääskeläinen

Haukka

et al. 2000

Eur. J. Inorg. Chem.

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The triarylphosphanes, (o‐thiomethylphenyl)diphenylphosphane (SP, 1), (o‐N,N′‐dimethylaminophenyl)diphenylphosphane (NP, 2), and (o‐methoxyphenyl)diphenylphosphane (OP, 3) have been structurally characterized. Detailed information on the stereochemistry of the ligands was gathered by spectroscopic (1H, 31P, 13C NMR) and X‐ray crystallographic studies. Molecular modeling methods for investigation of the structures were also applied. It is shown that the geometrical optimization of the ligand can be performed accurately by the ab initio Hartree−Fock method. Furthermore, the steric contribution of the coordinated ligands can be estimated by studying the different conformational states of the free ligands. The coordination abilities of the ligands were studied in reactions with the rhodium compounds Rh2(CO)4Cl2 and Rh(NO3)3 under different reaction conditions. The SP and NP ligands yielded mononuclear chelate complexes, while the OP ligand coordinated solely in a monodentate fashion through the phosphorus atom. The crystal structures of the ligands 1−3 and the rhodium(I) complexes [RhCl(CO)(NP)] (5) and [RhCl(CO)(OP)2] (6) are reported.

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Phosphorus-31 Nuclear Magnetic Resonance Spectra of Co-ordination Compounds

Cited by 154 publications

References 72 publications

Syntheses and 31P NMR studies of transition metal complexes containing derivatives of dioxaphospholane and dioxaphosphorinane

Syntheses and 31P NMR studies of transition metal complexes containing derivatives of dioxaphospholane and dioxaphosphorinane

Electrochemical and spectroscopic studies of tungstencarbonyl complexes containing nitrogen and phosphorous ligands

Structural and Theoretical Studies ofortho-Substituted Triphenylphosphane Ligands and Their Rhodium(I) Complexes

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